Structured organic films

ABSTRACT

A structured organic film comprising a plurality of segments and a plurality of linkers arranged as a covalent organic framework, wherein the structured organic film may be a multi-segment thick structured organic film.

This nonprovisional application claims the benefit of U.S. ProvisionalApplication No. 61/157,411, entitled “Structured Organic Films” filedMar. 4, 2009, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

Materials whose chemical structures are comprised of molecules linked bycovalent bonds into extended structures may be placed into two classes:(1) polymers and cross-linked polymers, and (2) covalent organicframeworks (also known as covalently linked organic networks).

The first class, polymers and cross-linked polymers, is typicallyembodied by polymerization of molecular monomers to form long linearchains of covalently-bonded molecules. Polymer chemistry processes canallow for polymerized chains to, in turn, or concomitantly, become‘cross-linked.’ The nature of polymer chemistry offers poor control overthe molecular-level structure of the formed material, i.e. theorganization of polymer chains and the patterning of molecular monomersbetween chains is mostly random. Nearly all polymers are amorphous, savefor some linear polymers that efficiently pack as ordered rods. Somepolymer materials, notably block co-polymers, can possess regions oforder within their bulk. In the two preceding cases the patterning ofpolymer chains is not by design, any ordering at the molecular-level isa consequence of the natural intermolecular packing tendencies.

The second class, covalent organic frameworks (COFs), differ from thefirst class (polymers/cross-linked polymers) in that COFs are intendedto be highly patterned. In COF chemistry molecular components are calledmolecular building blocks rather than monomers. During COF synthesismolecular building blocks react to form two- or three-dimensionalnetworks. Consequently, molecular building blocks are patternedthroughout COF materials and molecular building blocks are linked toeach other through strong covalent bonds.

COFs developed thus far are typically powders with high porosity and arematerials with exceptionally low density. COFs can store near-recordamounts of argon and nitrogen. While these conventional COFs are useful,there is a need, addressed by embodiments of the present invention, fornew materials that offer advantages over conventional COFs in terms ofenhanced characteristics.

The properties and characteristics of conventional COFs are described inthe following documents:

Yaghi et al., U.S. Pat. No. 7,582,798;

Yaghi et al., U.S. Pat. No. 7,196,210;

Shun Wan et al., “A Belt-Shaped, Blue Luminescent, and SemiconductingCovalent Organic Framework,” Angew. Chem. Int. Ed., Vol. 47, pp.8826-8830 (published on web Jan. 10, 2008);

Nikolas A. A. Zwaneveld et al., “Organized Formation of 2D ExtendedCovalent Organic Frameworks at Surfaces,” J. Am. Chem. Soc., Vol. 130,pp. 6678-6679 (published on web Apr. 30, 2008);

Adrien P. Cote et al., “Porous, Crystalline, Covalent OrganicFrameworks,” Science, Vol. 310, pp. 1166-1170 (Nov. 18, 2005);

Hani El-Kaderi et al., “Designed Synthesis of 3D Covalent OrganicFrameworks,” Science, Vol. 316, pp. 268-272 (Apr. 13, 2007);

Adrien P. Cote et al., “Reticular Synthesis of Microporous andMesoporous Covalent Organic Frameworks” J. Am. Chem. Soc., Vol. 129,12914-12915 (published on web Oct. 6, 2007);

Omar M. Yaghi et al., “Reticular synthesis and the design of newmaterials,” Nature, Vol. 423, pp. 705-714 (Jun. 12, 2003);

Nathan W. Ockwig et al., “Reticular Chemistry: Occurrence and Taxonomyof Nets and Grammar for the Design of Frameworks,” Acc. Chem. Res., Vol.38, No. 3, pp. 176-182 (published on web Jan. 19, 2005);

Pierre Kuhn et al., ‘Porous, Covalent Triazine-Based Frameworks Preparedby Ionothermal Synthesis,” Angew. Chem. Int. Ed., Vol. 47, pp.3450-3453. (Published on web Mar. 10, 2008);

Jia-Xing Jiang et al., “Conjugated Microporous Poly(aryleneethylnylene)Networks,” Angew. Chem. Int. Ed, Vol. 46, (2008) pp, 1-5 (Published onweb Sep. 26, 2008); and

Hunt, J. R. et al. “Reticular Synthesis of Covalent-Organic BorosilicateFrameworks” J. Am. Chem. Soc., Vol. 130, (2008), 11872-11873. (publishedon web Aug. 16, 2008).

SUMMARY OF THE DISCLOSURE

There is provided in embodiments a structured organic film comprising aplurality of segments and a plurality of linkers arranged as a covalentorganic framework, wherein at a macroscopic level the covalent organicframework is a film.

BRIEF DESCRIPTION OF THE DRAWINGS

Other aspects of the present disclosure will become apparent as thefollowing description proceeds and upon reference to the followingfigures which represent illustrative embodiments:

FIG. 1 represents a simplified side view of an exemplary photoreceptorthat incorporates a SOF of the present disclosure.

FIG. 2 represents a simplified side view of a second exemplaryphotoreceptor that incorporates a SOF of the present disclosure.

FIG. 3 represents a simplified side view of a third exemplaryphotoreceptor that incorporates a SOF of the present disclosure.

FIG. 4 represents a simplified side view of a first exemplary thin filmtransistor that incorporates a SOF of the present disclosure.

FIG. 5 is a graphic representation that compares the Fourier transforminfrared spectral of the products of control experiments mixtures,wherein onlyN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine isadded to the liquid reaction mixture (top), wherein onlybenzene-1,4-dimethanol is added to the liquid reaction mixture (middle),and wherein the necessary components needed to form a patterned Type 2SOF are included into the liquid reaction mixture (bottom).

FIG. 6 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprisingN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine segments, p-xylylsegments, and ether linkers.

FIG. 7. is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprisingN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine segments, n-hexylsegments, and ether linkers.

FIG. 8 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprisingN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine segments,4,4′-(cyclohexane-1,1-diyl)diphenyl, and ether linkers.

FIG. 9 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprising of triphenylamine segmentsand ether linkers.

FIG. 10 is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprising triphenylamine segments,benzene segments, and imine linkers.

FIG. 11, is a graphic representation of a Fourier transform infraredspectrum of a free standing SOF comprising triphenylamine segments, andimine linkers.

FIG. 12 is a graphic representation of a photo-induced discharge curve(PIDC) illustrating the photoconductivity of a Type 1 structured organicfilm overcoat layer.

FIG. 13 is a graphic representation of a photo-induced discharge curve(PIDC) illustrating the photoconductivity of a Type 1 structured organicfilm overcoat layer containing wax additives.

FIG. 14 is a graphic representation of a photo-induced discharge curve(PIDC) illustrating the photoconductivity of a Type 2 structured organicfilm overcoat layer.

FIG. 15 is a graphic representation of two-dimensional X-ray scatteringdata for the SOFs produced in Examples 26 and 54.

Unless otherwise noted, the same reference numeral in different Figuresrefers to the same or similar feature.

DETAILED DESCRIPTION

“Structured organic film” (SOF) is a new term introduced by the presentdisclosure to refer to a COF that is a film at a macroscopic level. Theterm “SOF” refers to a covalent organic framework (COF) that is a filmat a macroscopic level. The phrase “macroscopic level” refers, forexample, to the naked eye view of the present SOFs. Although COFs are anetwork at the “microscopic level” or “molecular level” (requiring useof powerful magnifying equipment or as assessed using scatteringmethods), the present SOF is fundamentally different at the “macroscopiclevel” because the film is for instance orders of magnitude larger incoverage than a microscopic level COF network. SOFs described hereinhave macroscopic morphologies much different than typical COFspreviously synthesized. COFs previously synthesized were typicallyobtained as polycrystalline or particulate powders wherein the powder isa collection of at least thousands of particles (crystals) where eachparticle (crystal) can have dimensions ranging from nanometers tomillimeters. The shape of the particles can range from plates, spheres,cubes, blocks, prisms, etc. The composition of each particle (crystal)is the same throughout the entire particle while at the edges, orsurfaces of the particle, is where the segments of the covalently-linkedframework terminate. The SOFs described herein are not collections ofparticles. Instead, the SOFs of the present disclosure are at themacroscopic level substantially defect-free SOFs or defect-free SOFshaving continuous covalent organic frameworks that can extend overlarger length scales such as for instance much greater than a millimeterto lengths such as a meter and, in theory, as much as hundreds ofmeters. It will also be appreciated that SOFs tend to have large aspectratios where typically two dimensions of a SOF will be much larger thanthe third. SOFs have markedly fewer macroscopic edges and disconnectedexternal surfaces than a collection of COF particles.

In embodiments, a “substantially defect-free SOF” or “defect-free SOF”may be formed from a reaction mixture deposited on the surface of anunderlying substrate. The term “substantially defect-free SOF” refers,for example, to an SOF that may or may not be removed from theunderlying substrate on which it was formed and contains substantiallyno pinholes, pores or gaps greater than the distance between the coresof two adjacent segments per square cm; such as, for example, less than10 pinholes, pores or gaps greater than about 250 nanometers in diameterper cm², or less than 5 pinholes, pores or gaps greater than about 100nanometers in diameter per cm². The term “defect-free SOF” refers, forexample, to an SOF that may or may not be removed from the underlyingsubstrate on which it was formed and contains no pinholes, pores or gapsgreater than the distance between the cores of two adjacent segments permicron², such as no pinholes, pores or gaps greater than about 100Angstroms in diameter per micron², or no pinholes, pores or gaps greaterthan about 50 Angstroms in diameter per micron², or no pinholes, poresor gaps greater than about 20 Angstroms in diameter per micron².

In embodiments, the SOF comprises at least one atom of an element thatis not carbon, such at least one atom selected from the group consistingof hydrogen, oxygen, nitrogen, silicon, phosphorous, selenium, fluorine,boron, and sulfur. In further embodiments, the SOF is a boroxine-,borazine-, borosilicate-, and boronate ester-free SOF.

Molecular Building Block

The SOFs of the present disclosure comprise molecular building blockshaving a segment (S) and functional groups (Fg). Molecular buildingblocks require at least two functional groups (x≧2) and may comprise asingle type or two or more types of functional groups. Functional groupsare the reactive chemical moieties of molecular building blocks thatparticipate in a chemical reaction to link together segments during theSOF forming process. A segment is the portion of the molecular buildingblock that supports functional groups and comprises all atoms that arenot associated with functional groups. Further, the composition of amolecular building block segment remains unchanged after SOF formation.

Functional Group

Functional groups are the reactive chemical moieties of molecularbuilding blocks that participate in a chemical reaction to link togethersegments during the SOF forming process. Functional groups may becomposed of a single atom, or functional groups may be composed of morethan one atom. The atomic compositions of functional groups are thosecompositions normally associated with reactive moieties in chemicalcompounds. Non-limiting examples of functional groups include halogens,alcohols, ethers, ketones, carboxylic acids, esters, carbonates, amines,amides, imines, ureas, aldehydes, isocyanates, tosylates, alkenes,alkynes and the like.

Molecular building blocks contain a plurality of chemical moieties, butonly a subset of these chemical moieties are intended to be functionalgroups during the SOF forming process. Whether or not a chemical moietyis considered a functional group depends on the reaction conditionsselected for the SOF forming process. Functional groups (Fg) denote achemical moiety that is a reactive moiety, that is, a functional groupduring the SOF forming process.

In the SOF forming process the composition of a functional group will bealtered through the loss of atoms, the gain of atoms, or both the lossand the gain of atoms; or, the functional group may be lost altogether.In the SOF, atoms previously associated with functional groups becomeassociated with linker groups, which are the chemical moieties that jointogether segments. Functional groups have characteristic chemistries andthose of ordinary skill in the art can generally recognize in thepresent molecular building blocks the atom(s) that constitute functionalgroup(s). It should be noted that an atom or grouping of atoms that areidentified as part of the molecular building block functional group maybe preserved in the linker group of the SOF. Linker groups are describedbelow.

Segment

A segment is the portion of the molecular building block that supportsfunctional groups and comprises all atoms that are not associated withfunctional groups. Further, the composition of a molecular buildingblock segment remains unchanged after SOF formation. In embodiments, theSOF may contain a first segment having a structure the same as ordifferent from a second segment. In other embodiments, the structures ofthe first and/or second segments may be the same as or different from athird segment, forth segment, fifth segment, etc. A segment is also theportion of the molecular building block that can provide an inclinedproperty. Inclined properties are described later in the embodiments.

In specific embodiments, the segment of the SOF comprises at least oneatom of an element that is not carbon, such at least one atom selectedfrom the group consisting of hydrogen, oxygen, nitrogen, silicon,phosphorous, selenium, fluorine, boron, and sulfur.

Illustrated below are examples of molecular building blocks. In eachexample the portion of molecular building block identified as thesegment (S) and functional groups (Fg) is indicated.

Molecular Building Block with One Type of Functional Group.

Molecular Building Block with Two Types of Functional Group.

Molecular Building Block with Two Types of Functional Group.

Linker

A linker is a chemical moiety that emerges in a SOF upon chemicalreaction between functional groups present on the molecular buildingblocks (illustrated below).

A linker may comprise a covalent bond, a single atom, or a group ofcovalently bonded atoms. The former is defined as a covalent bond linkerand may be, for example, a single covalent bond or a double covalentbond and emerges when functional groups on all partnered building blocksare lost entirely. The latter linker type is defined as a chemicalmoiety linker and may comprise one or more atoms bonded together bysingle covalent bonds, double covalent bonds, or combinations of thetwo. Atoms contained in linking groups originate from atoms present infunctional groups on molecular building blocks prior to the SOF formingprocess. Chemical moiety linkers may be well-known chemical groups suchas, for example, esters, ketones, amides, imines, ethers, urethanes,carbonates, and the like, or derivatives thereof.

For example, when two hydroxyl (—OH) functional groups are used toconnect segments in a SOF via an oxygen atom, the linker would be theoxygen atom, which may also be described as an ether linker Inembodiments, the SOF may contain a first linker having a structure thesame as or different from a second linker. In other embodiments, thestructures of the first and/or second linkers may be the same as ordifferent from a third linker, etc.

In specific embodiments, the linker comprises at least one atom of anelement that is not carbon, such at least one atom selected from thegroup consisting of hydrogen, oxygen, nitrogen, silicon, phosphorous,selenium, fluorine, boron, and sulfur.

SOF Types

Three exemplary types of SOF are described below. These SOF types areexpressed in terms of segment and linker combinations. The namingassociated with a particular SOF type bears no meaning toward thecomposition of building blocks selected, or procedure used to synthesizea SOF, or the physical properties of the SOF.

Type 1 SOF: comprises one segment type and one linker type.

Type 2 SOF: comprises two segment types and one linker type.

Type 3 SOF: a plurality of segment types and/or a plurality of linkertypes.

In embodiments, a plurality of building block types may be employed in asingle process to generate a SOF, which in turn would contain aplurality of segment types so long as the reactivity between buildingblock functional groups remains compatible. A SOF comprising a pluralityof segment types and/or a plurality of linker types is described as aType 3 SOF.

For example, among the various possibilities for Type 3 SOFs, a Type 3SOF may comprise a plurality of linkers including at least a firstlinker and a second linker (and optionally a third, forth, or fifth,etc., linker) that are different in structure, and a plurality ofsegments including at least a first segment and a second segment (andoptionally a third, forth, or fifth, etc., segment) that are differentin structure, where the first segment, when it is not at the edge of theSOF, is connected to at least three other segments (such as three of thesecond segments being connected via linkers to a first segment), whereinat least one of the connections is via the first linker and at least oneof the connections is via the second linker; or a Type 3 SOF maycomprise a plurality of linkers including at least a first linker and asecond linker (and optionally a third, forth, or fifth, etc., linker)that are different in structure, and a plurality of segments consistingof segments having an identical structure, where the segments that arenot at the edges of the SOF are connected by linkers to at least threeother segments, where at least one of the connections is via the firstlinker, and at least one of the connections is via the second linker; ora Type 3 SOF may comprise a plurality of segments including at least afirst segment and a second segment (and optionally a third, forth, orfifth, etc., segment) that are different in structure, where the firstsegment, when it is not at the edge of the SOF, is connected to at leastthree other segments (such as three second segments or various othersegments that are present) by one or more linkers.

Illustration of SOF Types

Described below are non-limiting examples for strategies to synthesize aspecific SOF type with exemplary chemical structures. From theillustrations below, it is made clear here that it is possible that thesame SOF type may be synthesized using different sets of molecularbuilding blocks. In each of the strategies provided below only afragment of the chemical structure of the SOF is displayed.

Strategy 1: Production of a Type 1 SOF Using One Type of MolecularBuilding Block. This SOF Contains an Ethylene (Two Atom) Linker Type.

Strategy 2: Production of a Type 1 SOF Using One Type of MolecularBuilding Block. This SOF Contains a Single Atom Linker Type.

Strategy 3: Production of a Type 1 SOF Using Two Types of MolecularBuilding Blocks Wherein the Segments are the Same. This SOF Contains aimine (Two Atom) Linker Type.

Strategy 4: Production of a Type 2 SOF Using Two Types of MolecularBuilding Block. This SOF Contains Two Segment Types and a Single LinkerType (Amide, Four Atoms).

Strategy 5: Production of a Type 3 SOF Using Two Types of MolecularBuilding Block. In this Case the Number of Segments is Two and theNumber of Linker Types is Two. In Addition, the SOF has PatternedSegments Linked by Imine (Three Atoms) and Amide (Four Atoms) Linkers.

Metrical Parameters of SOFs

SOFs have any suitable aspect ratio. In embodiments, SOFs have aspectratios for instance greater than about 30:1 or greater than about 50:1,or greater than about 70:1, or greater than about 100:1, such as about1000:1. The aspect ratio of a SOF is defined as the ratio of its averagewidth or diameter (that is, the dimension next largest to its thickness)to its average thickness (that is, its shortest dimension). The term‘aspect ratio,’ as used here, is not bound by theory. The longestdimension of a SOF is its length and it is not considered in thecalculation of SOF aspect ratio.

Generally, SOFs have widths and lengths, or diameters greater than about500 micrometers, such as about 10 mm, or 30 mm. The SOFs have thefollowing illustrative thicknesses: about 10 Angstroms to about 250Angstroms, such as about 20 Angstroms to about 200 Angstroms, for amono-segment thick layer and about 20 nm to about 5 nm, about 50 nm toabout 10 mm for a multi-segment thick layer.

SOF dimensions may be measured using a variety of tools and methods. Fora dimension about 1 micrometer or less, scanning electron microscopy isthe preferred method. For a dimension about 1 micrometer or greater, amicrometer (or ruler) is the preferred method.

Optional Periodicity of SOFs

SOFs may be isolated in crystalline or non-crystalline forms. Acrystalline film is one having sufficient periodicity at any lengthscale such that it can coherently scatter (diffract) electromagneticradiation, such as, for example, X-rays, and/or subatomic particles,such as, for example neutrons. Coherent scattering will be evidenced asan observed diffraction pattern as detected in 1-, 2-, or 3-dimensionsusing a detection system suited to detect the radiation or particleemployed. A non-crystalline film is one which does not coherentlyscatter (diffract) electromagnetic radiation, such as, for example,X-rays, and/or subatomic particles, such as, for example, neutrons.

All tools in the field of diffractometry, or tools that have a secondarycapability to collect scattering data, are available for measuringcoherent and non-coherent scattering. Such tools include, but are notlimited to, 1-, 2-, 3-, or 4-circle goniometers equipped with point,line, or area detection systems capable of detecting scattering(electromagnetic and/or subatomic) in 1-, 2-, or 3-dimensions, imagingtools such as, but are not limited to, electron microscopes equipped todetect scattered electrons from materials.

Alternatively, imaging methods capable of mapping structures at micronand submicron scales may be employed to assess the periodicity of a SOF.Such methods include, but are not limited to, scanning electronmicroscopy, tunneling electron microscopy, and atomic force microscopy.

Multilayer SOFs

A SOF may comprise a single layer or a plurality of layers (that is,two, three or more layers). SOFs that are comprised of a plurality oflayers may be physically joined (e.g., dipole and hydrogen bond) orchemically joined. Physically attached layers are characterized byweaker interlayer interactions or adhesion; therefore physicallyattached layers may be susceptible to delamination from each other.Chemically attached layers are expected to have chemical bonds (e.g.,covalent or ionic bonds) or have numerous physical or intermolecular(supramolecular) entanglements that strongly link adjacent layers.

Therefore, delamination of chemically attached layers is much moredifficult. Chemical attachments between layers may be detected usingspectroscopic methods such as focusing infrared or Raman spectroscopy,or with other methods having spatial resolution that can detect chemicalspecies precisely at interfaces. In cases where chemical attachmentsbetween layers are different chemical species than those within thelayers themselves it is possible to detect these attachments withsensitive bulk analyses such as solid-state nuclear magnetic resonancespectroscopy or by using other bulk analytical methods.

In the embodiments, the SOF may be a single layer (mono-segment thick ormulti-segment thick) or multiple layers (each layer being mono-segmentthick or multi-segment thick). “Thickness” refers, for example, to thesmallest dimension of the film. As discussed above, in a SOF, segmentsare molecular units that are covalently bonded through linkers togenerate the molecular framework of the film. The thickness of the filmmay also be defined in terms of the number of segments that is countedalong that axis of the film when viewing the cross-section of the film.A “monolayer” SOF is the simplest case and refers, for example, to wherea film is one segment thick. A SOF where two or more segments existalong this axis is referred to as a “multi-segment” thick SOF.

An exemplary method for preparing physically attached multilayer SOFsincludes: (1) forming a base SOF layer that may be cured by a firstcuring cycle, and (2) forming upon the base layer a second reactive wetlayer followed by a second curing cycle and, if desired, repeating thesecond step to form a third layer, a forth layer and so on. Thephysically stacked multilayer SOFs may have thicknesses greater thanabout 20 Angstroms such as, for example, the following illustrativethicknesses: about 20 Angstroms to about 10 cm, such as about 1 nm toabout 10 mm, or about 0.1 mm Angstroms to about 5 mm. In principle thereis no limit with this process to the number of layers that may bephysically stacked.

In embodiments, a multilayer SOF is formed by a method for preparingchemically attached multilayer SOFs by: (1) forming a base SOF layerhaving functional groups present on the surface (or dangling functionalgroups) from a first reactive wet layer, and (2) forming upon the baselayer a second SOF layer from a second reactive wet layer that comprisesmolecular building blocks with functional groups capable of reactingwith the dangling functional groups on the surface of the base SOFlayer. If desired, the formulation used to form the second SOF layershould comprise molecular building blocks with functional groups capableof reacting with the dangling functional groups from the base layer aswell as additional functional groups that will allow for a third layerto be chemically attached to the second layer. The chemically stackedmultilayer SOFs may have thicknesses greater than about 20 Angstromssuch as, for example, the following illustrative thicknesses: about 20Angstroms to about 10 cm, such as about 1 nm to about 10 mm, or about0.1 mm Angstroms to about 5 mm. In principle there is no limit with thisprocess to the number of layers that may be chemically stacked.

In embodiments, the method for preparing chemically attached multilayerSOFs comprises promoting chemical attachment of a second SOF onto anexisting SOF (base layer) by using a small excess of one molecularbuilding block (when more than one molecular building block is present)during the process used to form the SOF (base layer) whereby thefunctional groups present on this molecular building block will bepresent on the base layer surface. The surface of base layer may betreated with an agent to enhance the reactivity of dangling functionalgroups or to create an increased number of dangling functional groups.

In an embodiment the dangling functional groups present on the surfaceof an SOF may be altered to increase the propensity for covalentattachment (or, alternatively, to disfavor covalent attachment) ofparticular classes of molecules or individual molecules, such as SOFs,to a base layer or any additional substrate or SOF layer. For example,the surface of a base layer, such as an SOF layer, which may containreactive dangling functional groups, may be rendered pacified throughsurface treatment with a capping chemical group. For example, a SOFlayer having dangling hydroxyl alcohol groups may be pacified bytreatment with trimethylsiylchloride thereby capping hydroxyl groups asstable trimethylsilylethers. Alternatively, the surface of base layermay be treated with a non-chemically bonding agent, such as a wax, toblock reaction with dangling functional groups from subsequent layers.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

Drawn below are building blocks whose symmetrical elements are outlined.Such symmetrical elements are found in building blocks used in thepresent disclosure.

In embodiments, the Type 1 SOF contains segments, which are not locatedat the edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks. In embodiments, Type 2 and 3 SOF contains at least one segmenttype, which are not located at the edges of the SOF, that are connectedby linkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Molecular Building Block Enumeration

Illustrated below is a list of classes of exemplary molecular entitiesand examples of members of each class that may serve as molecularbuilding blocks for SOFs of the present disclosure.

Building blocks containing a carbon or silicon atomic core:

Building blocks containing alkoxy cores:

Building blocks containing a nitrogen or phosphorous atomic cores:

Building blocks containing aryl cores:

Building blocks containing carbonate cores:

Building blocks containing carbocyclic-, carbobicyclic-, orcarbotricyclic core:

Building blocks containing an oligothiophene core

Where Q may be independently selected from:

-   Aryl, biaryl, triaryl, and naphthyl, optionally substituted with    C1-C8 branched and unbranched alkyl, branched and unbranched C1-C8    perfluroalkyl, C1-C6 carbocylic, amino, hydroxyl, halogen, cyano,    nitro, ketone, carboxylic acid, carboxylic ester, mercaptyl,    thioether;-   Aryl, biaryl, triaryl, naphthyl, containing 1-3 heteoratoms per    ring, optionally substituted with C1-C8 branched and unbranched    alkyl, branched and unbranched C1-C8 perfluroalkyl, C1-C6    carbocylic, amino, hydroxyl, halogen, cyano, nitro, carboxylic acid,    carboxylic ester, mercaptyl, thioether;-   branched and unbranched C1-C8 perfluroalkyl, C1-C6 carbocylic,    amino, hydroxyl, halogen, cyano, nitro, carboxylic acid, ketone,    carboxylic ester, mercaptyl, thioether, alkyl ether, aryl ether;-   C1-C12 branched and unbranched alkyl;-   C1-C12 branched an unbranched perfluroalkyl;-   oligoether containing as many as 12 C—O units;-   with p of the Group IV atomic core ranging from about 1 to about 24,    such as from about 12 to about 24; x of the alkoxy cores ranging    from about 1 to about 12, such as from about 6 to about 12; z    ranging from about 1 to about 4, such as from about 2 to about 4; j    ranging from about 1 to about 12, such as from about 1 to about 12.-   Where Fg is a functional group, as defined earlier in the    embodiments, and may be independently selected from-   alcohol, alkyl or aryl ether, cyano, amino, halogen, ketone,    carboxylic acid, carboxylic acid ester, carboxylic acid chloride,    aryl or alkyl sulfonyl, formyl, hydrogen, and isocyanate.

Where R is independently selected from:

-   Aryl, biaryl, triaryl, and naphthyl, optionally substituted with    C1-C8 branched and unbranched alkyl, branched and unbranched C1-C8    perfluroalkyl, C1-C6 carbocylic, amino, hydroxyl, halogen, cyano,    nitro, ketone, carboxylic acid, carboxylic ester, mercaptyl,    thioether;-   Aryl, biaryl, triaryl, naphthyl, containing 1-3 heteratoms per ring    optionally substituted with C1-C8 branched and unbranched alkyl,    branched and unbranched C1-C8 perfluroalkyl, C1-C6 carbocylic,    amino, hydroxyl, halogen, cyano, nitro, ketone, carboxylic acid,    carboxylic ester, mercaptyl, thioether;-   branched and unbranched C1-C8 perfluroalkyl, C1-C6 carbocylic,    amino, hydroxyl, halogen, cyano, nitro, ketone, carboxylic acid,    carboxylic ester, mercaptyl, thioether, alkyl ether, aryl ether;-   C1-C12 branched and unbranched alkyl;-   C1-C12 branched an unbranched perfluroalkyl;-   oligoether containing as many as 12 C—O units;-   alcohol, alkyl or aryl ether, cyano, amino, halogen, carboxylic    acid, carboxylic acid ester, ketone, carboxylic acid chloride, aryl    or alkyl sulfonyl, formyl, hydrogen, isocyanate and the like.

Practice of Linking Chemistry

In embodiments linking chemistry may occur wherein the reaction betweenfunctional groups produces a volatile byproduct that may be largelyevaporated or expunged from the SOF during or after the film formingprocess or wherein no byproduct is formed. Linking chemistry may beselected to achieve a SOF for applications where the presence of linkingchemistry byproducts is not desired. Linking chemistry reactions mayinclude, for example, condensation, addition/elimination, and additionreactions, such as, for example, those that produce esters, imines,ethers, carbonates, urethanes, amides, acetals, and silyl ethers.

In embodiments the linking chemistry via a reaction between functiongroups producing a non-volatile byproduct that largely remainsincorporated within the SOF after the film forming process. Linkingchemistry in embodiments may be selected to achieve a SOF forapplications where the presence of linking chemistry byproducts does notimpact the properties or for applications where the presence of linkingchemistry byproducts may alter the properties of a SOF (such as, forexample, the electroactive, hydrophobic or hydrophilic nature of theSOF). Linking chemistry reactions may include, for example,substitution, metathesis, and metal catalyzed coupling reactions, suchas those that produce carbon-carbon bonds.

For all linking chemistry the ability to control the rate and extent ofreaction between building blocks via the chemistry between buildingblock functional groups is an important aspect of the presentdisclosure. Reasons for controlling the rate and extent of reaction mayinclude adapting the film forming process for different coating methodsand tuning the microscopic arrangement of building blocks to achieve aperiodic SOF, as defined in earlier embodiments.

Innate Properties of COFs

COFs have innate properties such as high thermal stability (typicallyhigher than 400° C. under atmospheric conditions); poor solubility inorganic solvents (chemical stability), and porosity (capable ofreversible guest uptake). In embodiments, SOFs may also possess theseinnate properties.

Added Functionality of SOFs

Added functionality denotes a property that is not inherent toconventional COFs and may occur by the selection of molecular buildingblocks wherein the molecular compositions provide the addedfunctionality in the resultant SOF. Added functionality may arise uponassembly of molecular building blocks having an “inclined property” forthat added functionality. Added functionality may also arise uponassembly of molecular building blocks having no “inclined property” forthat added functionality but the resulting SOF has the addedfunctionality as a consequence of linking segments (S) and linkers intoa SOF. Furthermore, emergence of added functionality may arise from thecombined effect of using molecular building blocks bearing an “inclinedproperty” for that added functionality whose inclined property ismodified or enhanced upon linking together the segments and linkers intoa SOF.

An Inclined Property of a Molecular Building Block

The term “inclined property” of a molecular building block refers, forexample, to a property known to exist for certain molecular compositionsor a property that is reasonably identifiable by a person skilled in artupon inspection of the molecular composition of a segment. As usedherein, the terms “inclined property” and “added functionality” refer tothe same general property (e.g., hydrophobic, electroactive, etc.) but“inclined property” is used in the context of the molecular buildingblock and “added functionality” is used in the context of the SOF.

The hydrophobic (superhydrophobic), hydrophilic, lipophobic(superlipophobic), lipophilic, and/or electroactive (conductor,semiconductor, charge transport material) nature of an SOF are someexamples of the properties that may represent an “added functionality”of an SOF.

The term hydrophobic (superhydrophobic) refers, for example, to theproperty of repelling water, or other polar species such as methanol, italso means an inability to absorb water and/or to swell as a result.Furthermore, hydrophobic implies an inability to form strong hydrogenbonds to water or other hydrogen bonding species. Hydrophobic materialsare typically characterized by having water contact angles greater than90° and superhydrophobic materials have water contact angles greaterthan 150° as measured using a contact angle goniometer or relateddevice.

The term hydrophilic refers, for example, to the property of attracting,adsorbing, or absorbing water or other polar species, or a surface thatis easily wetted by such species. Hydrophilic materials are typicallycharacterized by having less than 20° water contact angle as measuredusing a contact angle goniometer or related device. Hydrophilicity mayalso be characterized by swelling of a material by water or other polarspecies, or a material that can diffuse or transport water, or otherpolar species, through itself. Hydrophilicity, is further characterizedby being able to form strong or numerous hydrogen bonds to water orother hydrogen bonding species.

The term lipophobic (oleophobic) refers, for example, to the property ofrepelling oil or other non-polar species such as alkanes, fats, andwaxes. Lipophobic materials are typically characterized by having oilcontact angles greater than 90° as measured using a contact anglegoniometer or related device.

The term lipophilic (oleophilic) refers, for example, to the propertyattracting oil or other non-polar species such as alkanes, fats, andwaxes or a surface that is easily wetted by such species. Lipophilicmaterials are typically characterized by having a low to nil oil contactangle as measured using, for example, a contact angle goniometer.Lipophilicity can also be characterized by swelling of a material byhexane or other non-polar liquids.

The term electroactive refers, for example, to the property to transportelectrical charge (electrons and/or holes). Electroactive materialsinclude conductors, semiconductors, and charge transport materials.Conductors are defined as materials that readily transport electricalcharge in the presence of a potential difference. Semiconductors aredefined as materials do not inherently conduct charge but may becomeconductive in the presence of a potential difference and an appliedstimuli, such as, for example, an electric field, electromagneticradiation, heat, and the like. Charge transport materials are defined asmaterials that can transport charge when charge is injected from anothermaterial such as, for example, a dye, pigment, or metal in the presenceof a potential difference.

Conductors may be further defined as materials that give a signal usinga potentiometer from about 0.1 to about 10⁷ S/cm.

Semiconductors may be further defined as materials that give a signalusing a potentiometer from about 10⁻⁶ to about 10⁴ S/cm in the presenceof applied stimuli such as, for example an electric field,electromagnetic radiation, heat, and the like. Alternatively,semiconductors may be defined as materials having electron and/or holemobility measured using time-of-flight techniques in the range of 10⁻¹⁰to about 10⁶ cm²V⁻¹S⁻¹ when exposed to applied stimuli such as, forexample an electric field, electromagnetic radiation, heat, and thelike.

Charge transport materials may be further defined as materials that haveelectron and/or hole mobility measured using time-of-flight techniquesin the range of 10⁻¹⁰ to about 10⁶ cm²V⁻¹s⁻¹. It should be noted thatunder some circumstances charge transport materials may be alsoclassified as semiconductors.

SOFs with hydrophobic added functionality may be prepared by usingmolecular building blocks with inclined hydrophobic properties and/orhave a rough, textured, or porous surface on the sub-micron to micronscale. A paper describing materials having a rough, textured, or poroussurface on the sub-micron to micron scale being hydrophobic was authoredby Cassie and Baxter (Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc.,1944, 40, 546).

Molecular building blocks comprising or bearing highly-fluorinatedsegments have inclined hydrophobic properties and may lead to SOFs withhydrophobic added functionality. Highly-fluorinated segments are definedas the number of fluorine atoms present on the segment(s) divided by thenumber of hydrogen atoms present on the segment(s) being greater thanone. Fluorinated segments, which are not highly-fluorinated segments mayalso lead to SOFs with hydrophobic added functionality.

The above-mentioned fluorinated segments may include, for example,tetrafluorohydroquinone, perfluoroadipic acid hydrate,4,4′-(hexafluoroisopropylidene)diphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphenol, and the like.

SOFs having a rough, textured, or porous surface on the sub-micron tomicron scale may also be hydrophobic. The rough, textured, or porous SOFsurface can result from dangling functional groups present on the filmsurface or from the structure of the SOF. The type of pattern and degreeof patterning depends on the geometry of the molecular building blocksand the linking chemistry efficiency. The feature size that leads tosurface roughness or texture is from about 100 nm to about 10 μm, suchas from about 500 nm to about 5 μm.

SOFs with hydrophilic added functionality may be prepared by usingmolecular building blocks with inclined hydrophilic properties and/orcomprising polar linking groups.

Molecular building blocks comprising segments bearing polar substituentshave inclined hydrophilic properties and may lead to SOFs withhydrophilic added functionality. The term polar substituents refers, forexample, to substituents that can form hydrogen bonds with water andinclude, for example, hydroxyl, amino, ammonium, and carbonyl (such asketone, carboxylic acid, ester, amide, carbonate, urea).

SOFs with electroactive added functionality may be prepared by usingmolecular building blocks with inclined electroactive properties and/orbe electroactive resulting from the assembly of conjugated segments andlinkers. The following sections describe molecular building blocks withinclined hole transport properties, inclined electron transportproperties, and inclined semiconductor properties.

SOFs with hole transport added functionality may be obtained byselecting segment cores such as, for example, triarylamines, hydrazones(U.S. Pat. No. 7,202,002 B2 to Tokarski et al.), and enamines (U.S. Pat.No. 7,416,824 B2 to Kondoh et al.) with the following generalstructures:

The segment core comprising a triarylamine being represented by thefollowing general formula:

wherein Ar¹, Ar², Ar³, Ar⁴ and Ar⁵ each independently represents asubstituted or unsubstituted aryl group, or Ar⁵ independently representsa substituted or unsubstituted arylene group, and k represents 0 or 1,wherein at least two of Ar¹, Ar², Ar³, Ar⁴ and Ar⁵ comprises a Fg(previously defined). Ar⁵ may be further defined as, for example, asubstituted phenyl ring, substituted/unsubstituted phenylene,substituted/unsubstituted monovalently linked aromatic rings such asbiphenyl, terphenyl, and the like, or substituted/unsubstituted fusedaromatic rings such as naphthyl, anthranyl, phenanthryl, and the like.

Segment cores comprising arylamines with hole transport addedfunctionality include, for example, aryl amines such as triphenylamine,N,N,N′,N′-tetraphenyl-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-bis(4-butylphenyl)-N,N′-diphenyl-[p-terphenyl]-4,4″-diamine;hydrazones such as N-phenyl-N-methyl-3-(9-ethyl)carbazyl hydrazone and4-diethyl amino benzaldehyde-1,2-diphenyl hydrazone; and oxadiazolessuch as 2,5-bis(4-N,N′-diethylaminophenyl)-1,2,4-oxadiazole, stilbenes,and the like.

Molecular building blocks comprising triarylamine core segments withinclined hole transport properties may be derived from the list ofchemical structures including, for example, those listed below:

The segment core comprising a hydrazone being represented by thefollowing general formula:

wherein Ar¹, Ar², and Ar³ each independently represents an aryl groupoptionally containing one or more substituents, and R represents ahydrogen atom, an aryl group, or an alkyl group optionally containing asubstituent; wherein at least two of Ar¹, Ar², and Ar³ comprises a Fg(previously defined); and a related oxadiazole being represented by thefollowing general formula:

wherein Ar and Ar¹ each independently represent an aryl group thatcomprises a Fg (previously defined).

Molecular building blocks comprising hydrazone and oxadiazole coresegments with inclined hole transport properties may be derived from thelist of chemical structures including, for example, those listed below:

The segment core comprising an enamine being represented by thefollowing general formula:

wherein Ar¹, Ar², Ar³, and Ar⁴ each independently represents an arylgroup that optionally contains one or more substituents or aheterocyclic group that optionally contains one or more substituents,and R represents a hydrogen atom, an aryl group, or an alkyl groupoptionally containing a substituent; wherein at least two of Ar¹, Ar²,Ar³, and Ar⁴ comprises a Fg (previously defined).

Molecular building blocks comprising enamine core segments with inclinedhole transport properties may be derived from the list of chemicalstructures including, for example, those listed below:

SOFs with electron transport added functionality may be obtained byselecting segment cores comprising, for example, nitrofluorenones,9-fluorenylidene malonitriles, diphenoquinones, andnaphthalenetetracarboxylic diimides with the following generalstructures:

It should be noted that the carbonyl groups of diphenylquinones couldalso act as Fgs in the SOF forming process.

SOFs with semiconductor added functionality may be obtained by selectingsegment cores such as, for example, acenes,thiophenes/oligothiophenes/fused thiophenes, perylene bisimides, ortetrathiofulvalenes, and derivatives thereof with the following generalstructures:

The SOF may be a p-type semiconductor, n-type semiconductor or ambipolarsemiconductor. The SOF semiconductor type depends on the nature of themolecular building blocks. Molecular building blocks that possess anelectron donating property such as alkyl, alkoxy, aryl, and aminogroups, when present in the SOF, may render the SOF a p-typesemiconductor. Alternatively, molecular building blocks that areelectron withdrawing such as cyano, nitro, fluoro, fluorinated alkyl,and fluorinated aryl groups may render the SOF into the n-typesemiconductor.

Molecular building blocks comprising acene core segments with inclinedsemiconductor properties may be derived from the list of chemicalstructures including, for example, those listed below:

Molecular building blocks comprising thiophene/oligothiophene/fusedthiophene core segments with inclined semiconductor properties may bederived from the list of chemical structures including, for example,those listed below:

Examples of molecular building blocks comprising perylene bisimide coresegments with inclined semiconductor properties may be derived from thechemical structure below:

Molecular building blocks comprising tetrathiofulvalene core segmentswith inclined semiconductor properties may be derived from the list ofchemical structures including, for example, those listed below:

wherein Ar each independently represents an aryl group that optionallycontains one or more substituents or a heterocyclic group thatoptionally contains one or more substituents.

Similarly, the electroactivity of SOFs prepared by these molecularbuilding blocks will depend on the nature of the segments, nature of thelinkers, and how the segments are orientated within the SOF. Linkersthat favor preferred orientations of the segment moieties in the SOF areexpected to lead to higher electroactivity.

Process for Preparing a Structured Organic Film

The process for making SOFs typically comprises a number of activitiesor steps (set forth below) that may be performed in any suitablesequence or where two or more activities are performed simultaneously orin close proximity in time:

A process for preparing a structured organic film comprising:

-   (a) preparing a liquid-containing reaction mixture comprising a    plurality of molecular building blocks each comprising a segment and    a number of functional groups;-   (b) depositing the reaction mixture as a wet film;-   (c) promoting a change of the wet film including the molecular    building blocks to a dry film comprising the SOF comprising a    plurality of the segments and a plurality of linkers arranged as a    covalent organic framework, wherein at a macroscopic level the    covalent organic framework is a film;-   (d) optionally removing the SOF from the coating substrate to obtain    a free-standing SOF;-   (e) optionally processing the free-standing SOF into a roll;-   (f) optionally cutting and seaming the SOF into a belt; and-   (g) optionally performing the above SOF formation process(es) upon    an SOF (which was prepared by the above SOF formation process(es))    as a substrate for subsequent SOF formation process(es).

The above activities or steps may be conducted at atmospheric, superatmospheric, or subatmospheric pressure. The term “atmospheric pressure”as used herein refers to a pressure of about 760 torr. The term “superatmospheric” refers to pressures greater than atmospheric pressure, butless than 20 atm. The term “subatmospheric pressure” refers to pressuresless than atmospheric pressure. In an embodiment, the activities orsteps may be conducted at or near atmospheric pressure. Generally,pressures of from about 0.1 atm to about 2 atm, such as from about 0.5atm to about 1.5 atm, or 0.8 atm to about 1.2 atm may be convenientlyemployed.

Process Action A: Preparation of the Liquid-Containing Reaction Mixture

The reaction mixture comprises a plurality of molecular building blocksthat are dissolved, suspended, or mixed in a liquid. The plurality ofmolecular building blocks may be of one type or two or more types. Whenone or more of the molecular building blocks is a liquid, the use of anadditional liquid is optional. Catalysts may optionally be added to thereaction mixture to enable SOF formation or modify the kinetics of SOFformation during Action C described above. Additives or secondarycomponents may optionally be added to the reaction mixture to alter thephysical properties of the resulting SOF.

The reaction mixture components (molecular building blocks, optionally aliquid, optionally catalysts, and optionally additives) are combined ina vessel. The order of addition of the reaction mixture components mayvary; however, typically the catalyst is added last. In particularembodiments, the molecular building blocks are heated in the liquid inthe absence of the catalyst to aid the dissolution of the molecularbuilding blocks. The reaction mixture may also be mixed, stirred,milled, or the like, to ensure even distribution of the formulationcomponents prior to depositing the reaction mixture as a wet film.

In embodiments, the reaction mixture may be heated prior to beingdeposited as a wet film. This may aid the dissolution of one or more ofthe molecular building blocks and/or increase the viscosity of thereaction mixture by the partial reaction of the reaction mixture priorto depositing the wet layer. This approach may be used to increase theloading of the molecular building blocks in the reaction mixture.

In particular embodiments, the reaction mixture needs to have aviscosity that will support the deposited wet layer. Reaction mixtureviscosities range from about 10 to about 50,000 cps, such as from about25 to about 25,000 cps or from about 50 to about 1000 cps.

The molecular building block loading or “loading” in the reactionmixture is defined as the total weight of the molecular building blocksand optionally the catalysts divided by the total weight of the reactionmixture. Building block loadings may range from about 3 to 100%, such asfrom about 5 to about 50%, or from about 15 to about 40%. In the casewhere a liquid molecular building block is used as the only liquidcomponent of the reaction mixture (i.e. no additional liquid is used),the building block loading would be about 100%.

Liquids used in the reaction mixture may be pure liquids, such assolvents, and/or solvent mixtures. Liquids are used to dissolve orsuspend the molecular building blocks and catalyst/modifiers in thereaction mixture. Liquid selection is generally based on balancing thesolubility/dispersion of the molecular building blocks and a particularbuilding block loading, the viscosity of the reaction mixture, and theboiling point of the liquid, which impacts the promotion of the wetlayer to the dry SOF. Suitable liquids may have boiling points fromabout 30 to about 300° C., such as from about 65° C. to about 250° C.,or from about 100° C. to about 180° C.

Liquids can include molecule classes such as alkanes (hexane, heptane,octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane,decalin); mixed alkanes (hexanes, heptanes); branched alkanes(isooctane); aromatic compounds (toluene, o-, m-, p-xylene, mesitylene,nitrobenzene, benzonitrile, butylbenzene, aniline); ethers (benzyl ethylether, butyl ether, isoamyl ether, propyl ether); cyclic ethers(tetrahydrofuran, dioxane), esters (ethyl acetate, butyl acetate, butylbutyrate, ethoxyethyl acetate, ethyl propionate, phenyl acetate, methylbenzoate); ketones (acetone, methyl ethyl ketone, methyl isobutylketone,diethyl ketone, chloroacetone, 2-heptanone), cyclic ketones(cyclopentanone, cyclohexanone), amines (1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine;pyridine); amides (dimethylformamide, N-methylpyrolidinone,N,N-dimethylformamide); alcohols (methanol, ethanol, n-, i-propanol, n-,t-butanol, 1-methoxy-2-propanol, hexanol, cyclohexanol, 3-pentanol,benzyl alcohol); nitriles (acetonitrile, benzonitrile, butyronitrile),halogenated aromatics (chlorobenzene, dichlorobenzene,hexafluorobenzene), halogenated alkanes (dichloromethane, chloroform,dichloroethylene, tetrachloroethane); and water.

Mixed liquids comprising a first solvent, second solvent, third solvent,and so forth may also be used in the reaction mixture. Two or moreliquids may be used to aid the dissolution/dispersion of the molecularbuilding blocks; and/or increase the molecular building block loading;and/or allow a stable wet film to be deposited by aiding the wetting ofthe substrate and deposition instrument; and/or modulate the promotionof the wet layer to the dry SOF. In embodiments, the second solvent is asolvent whose boiling point or vapor-pressure curve or affinity for themolecular building blocks differs from that of the first solvent. Inembodiments, a first solvent has a boiling point higher than that of thesecond solvent. In embodiments, the second solvent has a boiling pointequal to or less than about 100° C., such as in the range of from about30° C. to about 100° C., or in the range of from about 40° C. to about90° C., or about 50° C. to about 80° C.

In embodiments, the first solvent, or higher boiling point solvent, hasa boiling point equal to or greater than about 65° C., such as in therange of from about 80° C. to about 300° C., or in the range of fromabout 100° C. to about 250° C., or about 100° C. to about 180° C. Thehigher boiling point solvent may include, for example, the following thevalue in parentheses is the boiling point of the compound): hydrocarbonsolvents such as amylbenzene (202° C.), isopropylbenzene (152° C.),1,2-diethylbenzene (183° C.), 1,3-diethylbenzene (181° C.),1,4-diethylbenzene (184° C.), cyclohexylbenzene (239° C.), dipentene(177° C.), 2,6-dimethylnaphthalene (262° C.), p-cymene (177° C.),camphor oil (160-185° C.), solvent naphtha (110-200° C.), cis-decalin(196° C.), trans-decalin (187° C.), decane (174° C.), tetralin (207°C.), turpentine oil (153-175° C.), kerosene (200-245° C.), dodecane(216° C.), dodecylbenzene (branched), and so forth; ketone and aldehydesolvents such as acetophenone (201.7° C.), isophorone (215.3° C.),phorone (198-199° C.), methylcyclohexanone (169.0-170.5° C.), methyln-heptyl ketone (195.3° C.), and so forth; ester solvents such asdiethyl phthalate (296.1° C.), benzyl acetate (215.5° C.),γ-butyrolactone (204° C.), dibutyl oxalate (240° C.), 2-ethylhexylacetate (198.6° C.), ethyl benzoate (213.2° C.), benzyl formate (203°C.), and so forth; diethyl sulfate (208° C.), sulfolane (285° C.), andhalohydrocarbon solvents; etherified hydrocarbon solvents; alcoholsolvents; ether/acetal solvents; polyhydric alcohol solvents; carboxylicanhydride solvents; phenolic solvents; water; and silicone solvents.

The ratio of the mixed liquids may be established by one skilled in theart. The ratio of liquids a binary mixed liquid may be from about 1:1 toabout 99:1, such as from about 1:10 to about 10:1, or about 1:5 to about5:1, by volume. When n liquids are used, with n ranging from about 3 toabout 6, the amount of each liquid ranges from about 1% to about 95%such that the sum of each liquid contribution equals 100%.

In embodiments, the mixed liquid comprises at least a first and a secondsolvent with different boiling points. In further embodiments, thedifference in boiling point between the first and the second solvent maybe from about nil to about 150° C., such as from nil to about 50° C. Forexample, the boiling point of the first solvent may exceed the boilingpoint of the second solvent by about 1° C. to about 150° C., such as byabout 5° C. to about 100° C., or by about 10° C. to about 50° C.

Mixed liquids may be used to slow the rate of conversion of the wetlayer to the SOF in order to manipulate the characteristics of the SOFs.For condensation and addition/elimination linking chemistries, liquidssuch as water, 1°, 2′, or 3° alcohols (such as methanol, ethanol,propanol, isopropanol, butanol, 1-methoxy-2-propanol, tert-butanol) maybe used.

Optionally a catalyst may be present in the reaction mixture to assistthe promotion of the wet layer to the dry SOF. Selection and use of theoptional catalyst depends on the functional groups on the molecularbuilding blocks. Catalysts may be homogeneous (dissolved) orheterogeneous (undissolved or partially dissolved) and include Brönstedacids (HCl (aq), acetic acid, p-toluenesulfonic acid, amine-protectedp-toluenesulfonic acid such as pyrridium p-toluenesulfonate,trifluoroacetic acid); Lewis acids (boron trifluoroetherate, aluminumtrichloride); Brönsted bases (metal hydroxides such as sodium hydroxide,lithium hydroxide, potassium hydroxide; 1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine);Lewis bases (N,N-dimethyl-4-aminopyridine); metals (Cu bronze); metalsalts (FeCl₃, AuCl₃); and metal complexes (ligated palladium complexes,ligated ruthenium catalysts). Typical catalyst loading ranges from about0.01% to about 25%, such as from about 0.1% to about 5% of the molecularbuilding block loading in the reaction mixture. The catalyst may or maynot be present in the final SOF composition.

Optionally additives or secondary components may be present in thereaction mixture and wet layer. Such additives or secondary componentsmay also be integrated into a dry SOF. Additives or secondary componentscan be homogeneous or heterogeneous in the reaction mixture and wetlayer or in a dry SOF. The terms “additive” or “secondary component,”refer, for example, to atoms or molecules that are not covalently boundin the SOF, but are randomly distributed in the composition. Additivesmay be used to alter the physical properties of the SOF such aselectrical properties (conductivity, semiconductivity, electrontransport, hole transport), surface energy (hydrophobicity,hydrophilicity), tensile strength, thermal conductivity, impactmodifiers, reinforcing fibers, antiblocking agents, lubricants,antistatic agents, coupling agents, wetting agents, antifogging agents,flame retardants, ultraviolet stabilizers, antioxidants, biocides, dyes,pigments, odorants, deodorants, nucleating agents and the like.

Process Action B: Depositing the Reaction Mixture as a Wet Film

The reaction mixture may be applied as a wet film to a variety ofsubstrates using a number of liquid deposition techniques. The thicknessof the SOF is dependant on the thickness of the wet film and themolecular building block loading in the reaction mixture. The thicknessof the wet film is dependent on the viscosity of the reaction mixtureand the method used to deposit the reaction mixture as a wet film.

Substrates include, for example, polymers, papers, metals and metalalloys, doped and undoped forms of elements from Groups III-VI of theperiodic table, metal oxides, metal chalcogenides, and previouslyprepared SOF films. Examples of polymer film substrates includepolyesters, polyolefins, polycarbonates, polystyrenes,polyvinylchloride, block and random copolymers thereof, and the like.Examples of metallic surfaces include metallized polymers, metal foils,metal plates; mixed material substrates such as metals patterned ordeposited on polymer, semiconductor, metal oxide, or glass substrates.Examples of substrates comprised of doped and undoped elements fromGroups III-VI of the periodic table include, aluminum, silicon, siliconn-doped with phosphorous, silicon p-doped with boron, tin, galliumarsenide, lead, gallium indium phosphide, and indium. Examples of metaloxides include silicon dioxide, titanium dioxide, indium tin oxide, tindioxide, selenium dioxide, and alumina. Examples of metal chalcogenidesinclude cadmium sulfide, cadmium telluride, and zinc selenide.Additionally, it is appreciated that chemically treated or mechanicallymodified forms of the above substrates remain within the scope ofsurfaces which may be coated with the reaction mixture.

In embodiments, the substrate may be composed of, for example, silicon,glass plate, plastic film or sheet. For structurally flexible devices, aplastic substrate such as polyester, polycarbonate, polyimide sheets andthe like may be used. The thickness of the substrate may be from around10 micrometers to over 10 millimeters with an exemplary thickness beingfrom about 50 to about 100 micrometers, especially for a flexibleplastic substrate, and from about 1 to about 10 millimeters for a rigidsubstrate such as glass or silicon.

The reaction mixture may be applied to the substrate using a number ofliquid deposition techniques including, for example, spin coating, bladecoating, web coating, dip coating, cup coating, rod coating, screenprinting, ink jet printing, spray coating, stamping and the like. Themethod used to deposit the wet layer depends on the nature, size, andshape of the substrate and the desired wet layer thickness. Thethickness of the wet layer can range from about 10 nm to about 5 mm,such as from about 100 nm to about 1 mm, or from about 1 μm to about 500μm.

Process Action C: Promoting the Change of Wet Film to the Dry SOF

The term “promoting” refers, for example, to any suitable technique tofacilitate a reaction of the molecular building blocks. In the casewhere a liquid needs to be removed to form the dry film, “promoting”also refers to removal of the liquid. Reaction of the molecular buildingblocks and removal of the liquid can occur sequentially or concurrently.In certain embodiments, the liquid is also one of the molecular buildingblocks and is incorporated into the SOF. The term “dry film” refers, forexample, to substantially dry films and in embodiments “dry film” mayalso refer, for example, to a liquid content less than about 5% byweight of the film.

Promoting the wet layer to form a dry SOF may be accomplished by anysuitable technique. Promoting the wet layer to form a dry SOF typicallyinvolves theonal treatment including, for example, oven drying, infraredradiation (IR), and the like with temperatures ranging from 40 to 350°C. and from 60 to 200° C. and from 85 to 160° C. The total heating timecan range from about four seconds to about 24 hours, such as from oneminute to 120 minutes, or from three minutes to 60 minutes.

IR promotion of the wet layer to the COF film may be achieved using anIR heater module mounted over a belt transport system. Various types ofIR emitters may be used, such as carbon IR emitters or short wave IRemitters (available from Heraerus). Additional exemplary informationregarding carbon IR emitters or short wave IR emitters is summarized inthe following Table.

Number of Module Power IR lamp Peak Wavelength lamps (kW) Carbon 2.0micron 2 - twin tube 4.6 Short wave 1.2-1.4 micron 3 - twin tube 4.5

Process Action D: Optionally Removing the SOF from the Coating substrateto Obtain a Free-Standing SOF

In embodiments, a free-standing SOF is desired. Free-standing SOFs maybe obtained when an appropriate low adhesion substrate is used tosupport the deposition of the wet layer. Appropriate substrates thathave low adhesion to the SOF may include, for example, metal foils,metalized polymer substrates, release papers and SOFs, such as SOFsprepared with a surface that has been altered to have a low adhesion ora decreased propensity for adhesion or attachment. Removal of the SOFfrom the supporting substrate may be achieved in a number of ways bysomeone skilled in the art. For example, removal of the SOF from thesubstrate may occur by starting from a corner or edge of the film andoptionally assisted by passing the substrate and SOF over a curvedsurface.

Process Action E: Optionally Processing the Free-Standing SOF into aRoll

Optionally, a free-standing SOF or a SOF supported by a flexiblesubstrate may be processed into a roll. The SOF may be processed into aroll for storage, handling, and a variety of other purposes. Thestarting curvature of the roll is selected such that the SOF is notdistorted or cracked during the rolling process.

Process Action F: Optionally Cutting and Seaming the SOF into a Shape,Such as a Belt

The method for cutting and seaming the SOF is similar to that describedin U.S. Pat. No. 5,455,136 issued on Oct. 3, 1995 (for polymer films),the disclosure of which is herein totally incorporated by reference. AnSOF belt may be fabricated from a single SOF, a multi layer SOF or anSOF sheet cut from a web. Such sheets may be rectangular in shape or anyparticular shape as desired. All sides of the SOF(s) may be of the samelength, or one pair of parallel sides may be longer than the other pairof parallel sides. The SOF(s) may be fabricated into shapes, such as abelt by overlap joining the opposite marginal end regions of the SOFsheet. A seam is typically produced in the overlapping marginal endregions at the point of joining. Joining may be affected by any suitablemeans. Typical joining techniques include, for example, welding(including ultrasonic), gluing, taping, pressure heat fusing and thelike. Methods, such as ultrasonic welding, are desirable general methodsof joining flexible sheets because of their speed, cleanliness (nosolvents) and production of a thin and narrow seam.

Process Action G: Optionally Using a SOF as a Substrate for SubsequentSOF Formation Processes

A SOF may be used as a substrate in the SOF forming process to afford amulti-layered structured organic film. The layers of a multi-layered SOFmay be chemically bound in or in physical contact. Chemically bound,multi-layered SOFs are formed when functional groups present on thesubstrate SOF surface can react with the molecular building blockspresent in the deposited wet layer used to form the second structuredorganic film layer. Multi-layered SOFs in physical contact may notchemically bound to one another.

A SOF substrate may optionally be chemically treated prior to thedeposition of the wet layer to enable or promote chemical attachment ofa second SOF layer to form a multi-layered structured organic film.

Alternatively, a SOF substrate may optionally be chemically treatedprior to the deposition of the wet layer to disable chemical attachmentof a second SOF layer (surface pacification) to form a physical contactmulti-layered SOF.

Other methods, such as lamination of two or more SOFs, may also be usedto prepare physically contacted multi-layered SOFs.

Applications of SOFs

SOFs may be used in for instance electronic devices such as solar cells,radio frequency identification tags, organic light emitting devices,photoreceptors, thin film transistors and the like.

Application A: SOFs in Photoreceptor Layers

Representative structures of an electrophotographic imaging member(e.g., a photoreceptor) are shown in FIGS. 1-3. These imaging membersare provided with an anti-curl layer 1, a supporting substrate 2, anelectrically conductive ground plane 3, a charge blocking layer 4, anadhesive layer 5, a charge generating layer 6, a charge transport layer7, an overcoating layer 8, and a ground strip 9. In FIG. 3, imaginglayer 10 (containing both charge generating material and chargetransport material) takes the place of separate charge generating layer6 and charge transport layer 7.

As seen in the figures, in fabricating a photoreceptor, a chargegenerating material (CGM) and a charge transport material (CTM) may bedeposited onto the substrate surface either in a laminate typeconfiguration where the CGM and CTM are in different layers (e.g., FIGS.1 and 2) or in a single layer configuration where the CGM and CTM are inthe same layer (e.g., FIG. 3). In embodiments, the photoreceptors may beprepared by applying over the electrically conductive layer the chargegeneration layer 6 and, optionally, a charge transport layer 7. Inembodiments, the charge generation layer and, when present, the chargetransport layer, may be applied in either order.

Anti Curl Layer

For some applications, an optional anti-curl layer 1, which comprisesfilm-forming organic or inorganic polymers that are electricallyinsulating or slightly semi-conductive, may be provided. The anti-cudlayer provides flatness and/or abrasion resistance.

Anti-curl layer 1 may be formed at the back side of the substrate 2,opposite the imaging layers. The anti-curl layer may include, inaddition to the film-forming resin, an adhesion promoter polyesteradditive. Examples of film-forming resins useful as the anti-curl layerinclude, but are not limited to, polyacrylate, polystyrene,poly(4,4′-isopropylidene diphenylcarbonate), poly(4,4′-cyclohexylidenediphenylcarbonate), mixtures thereof and the like.

Additives may be present in the anti-curl layer in the range of about0.5 to about 40 weight percent of the anti-curl layer. Additives includeorganic and inorganic particles that may further improve the wearresistance and/or provide charge relaxation property. Organic particlesinclude Teflon powder, carbon black, and graphite particles. Inorganicparticles include insulating and semiconducting metal oxide particlessuch as silica, zinc oxide, tin oxide and the like. Anothersemiconducting additive is the oxidized oligomer salts as described inU.S. Pat. No. 5,853,906. The oligomer salts are oxidizedN,N,N′,N′-tetra-p-tolyl-4,4′-biphenyldiamine salt.

Typical adhesion promoters useful as additives include, but are notlimited to, duPont 49,000 (duPont), Vitel PE-100, Vitel PE-200, VitelPE-307 (Goodyear), mixtures thereof and the like. Usually from about 1to about 15 weight percent adhesion promoter is selected forfilm-forming resin addition, based on the weight of the film-formingresin.

The thickness of the anti-curl layer is typically from about 3micrometers to about 35 micrometers, such as from about 10 micrometersto about 20 micrometers, or about 14 micrometers.

The anti-curl coating may be applied as a solution prepared bydissolving the film-forming resin and the adhesion promoter in a solventsuch as methylene chloride. The solution may be applied to the rearsurface of the supporting substrate (the side opposite the imaginglayers) of the photoreceptor device, for example, by web coating or byother methods known in the art. Coating of the overcoat layer and theanti-curl layer may be accomplished simultaneously by web coating onto amultilayer photoreceptor comprising a charge transport layer, chargegeneration layer, adhesive layer, blocking layer, ground plane andsubstrate. The wet film coating is then dried to produce the anti-curllayer 1.

The Supporting Substrate

As indicated above, the photoreceptors are prepared by first providing asubstrate 2, i.e., a support. The substrate may be opaque orsubstantially transparent and may comprise any additional suitablematerial(s) having given required mechanical properties, such as thosedescribed in U.S. Pat. Nos. 4,457,994; 4,871,634; 5,702,854; 5,976,744;and 7,384,717 the disclosures of which are incorporated herein byreference in their entireties.

The substrate may comprise a layer of electrically non-conductivematerial or a layer of electrically conductive material, such as aninorganic or organic composition. If a non-conductive material isemployed, it may be necessary to provide an electrically conductiveground plane over such non-conductive material. If a conductive materialis used as the substrate, a separate ground plane layer may not benecessary.

The substrate may be flexible or rigid and may have any of a number ofdifferent configurations, such as, for example, a sheet, a scroll, anendless flexible belt, a web, a cylinder, and the like. Thephotoreceptor may be coated on a rigid, opaque, conducting substrate,such as an aluminum drum.

Various resins may be used as electrically non-conducting materials,including, for example, polyesters, polycarbonates, polyamides,polyurethanes, and the like. Such a substrate may comprise acommercially available biaxially oriented polyester known as MYLAR™,available from E. I. duPont de Nemours & Co., MELINEX™, available fromICI Americas Inc., or HOSTAPHAN™, available from American HoechstCorporation. Other materials of which the substrate may be comprisedinclude polymeric materials, such as polyvinyl fluoride, available asTEDLAR™ from E. I. duPont de Nemours & Co., polyethylene andpolypropylene, available as MARLEX™ from Phillips Petroleum Company,polyphenylene sulfide, RYTON™ available from Phillips Petroleum Company,and polyimides, available as KAPTON™ from E. I. duPont de Nemours & Co.The photoreceptor may also be coated on an insulating plastic drum,provided a conducting ground plane has previously been coated on itssurface, as described above. Such substrates may either be seamed orseamless.

When a conductive substrate is employed, any suitable conductivematerial may be used. For example, the conductive material can include,but is not limited to, metal flakes, powders or fibers, such asaluminum, titanium, nickel, chromium, brass, gold, stainless steel,carbon black, graphite, or the like, in a binder resin including metaloxides, sulfides, silicides, quaternary ammonium salt compositions,conductive polymers such as polyacetylene or its pyrolysis and moleculardoped products, charge transfer complexes, and polyphenyl silane andmolecular doped products from polyphenyl silane. A conducting plasticdrum may be used, as well as the conducting metal drum made from amaterial such as aluminum.

The thickness of the substrate depends on numerous factors, includingthe required mechanical performance and economic considerations. Thethickness of the substrate is typically within a range of from about 65micrometers to about 150 micrometers, such as from about 75 micrometersto about 125 micrometers for optimum flexibility and minimum inducedsurface bending stress when cycled around small diameter rollers, e.g.,19 mm diameter rollers. The substrate for a flexible belt may be ofsubstantial thickness, for example, over 200 micrometers, or of minimumthickness, for example, less than 50 micrometers, provided there are noadverse effects on the final photoconductive device. Where a drum isused, the thickness should be sufficient to provide the necessaryrigidity. This is usually about 1-6 mm.

The surface of the substrate to which a layer is to be applied may becleaned to promote greater adhesion of such a layer. Cleaning may beeffected, for example, by exposing the surface of the substrate layer toplasma discharge, ion bombardment, and the like. Other methods, such assolvent cleaning, may also be used.

Regardless of any technique employed to form a metal layer, a thin layerof metal oxide generally forms on the outer surface of most metals uponexposure to air. Thus, when other layers overlying the metal layer arecharacterized as “contiguous” layers, it is intended that theseoverlying contiguous layers may, in fact, contact a thin metal oxidelayer that has formed on the outer surface of the oxidizable metallayer.

The Electrically Conductive Ground Plane

As stated above, in embodiments, the photoreceptors prepared comprise asubstrate that is either electrically conductive or electricallynon-conductive. When a non-conductive substrate is employed, anelectrically conductive ground plane 3 must be employed, and the groundplane acts as the conductive layer. When a conductive substrate isemployed, the substrate may act as the conductive layer, although aconductive ground plane may also be provided.

If an electrically conductive ground plane is used, it is positionedover the substrate. Suitable materials for the electrically conductiveground plane include, for example, aluminum, zirconium, niobium,tantalum, vanadium, hafnium, titanium, nickel, stainless steel,chromium, tungsten, molybdenum, copper, and the like, and mixtures andalloys thereof. In embodiments, aluminum, titanium, and zirconium may beused.

The ground plane may be applied by known coating techniques, such assolution coating, vapor deposition, and sputtering. A method of applyingan electrically conductive ground plane is by vacuum deposition. Othersuitable methods may also be used.

In embodiments, the thickness of the ground plane may vary over asubstantially wide range, depending on the optical transparency andflexibility desired for the electrophotoconductive member. For example,for a flexible photoresponsive imaging device, the thickness of theconductive layer may be between about 20 angstroms and about 750angstroms; such as, from about 50 angstroms to about 200 angstroms foran optimum combination of electrical conductivity, flexibility, andlight transmission. However, the ground plane can, if desired, beopaque.

The Charge Blocking Layer

After deposition of any electrically conductive ground plane layer, acharge blocking layer 4 may be applied thereto. Electron blocking layersfor positively charged photoreceptors permit holes from the imagingsurface of the photoreceptor to migrate toward the conductive layer. Fornegatively charged photoreceptors, any suitable hole blocking layercapable of forming a barrier to prevent hole injection from theconductive layer to the opposite photoconductive layer may be utilized.

If a blocking layer is employed, it may be positioned over theelectrically conductive layer. The term “over,” as used herein inconnection with many different types of layers, should be understood asnot being limited to instances wherein the layers are contiguous.Rather, the term “over” refers, for example, to the relative placementof the layers and encompasses the inclusion of unspecified intermediatelayers.

The blocking layer 4 may include polymers such as polyvinyl butyral,epoxy resins, polyesters, polysiloxanes, polyamides, polyurethanes, andthe like; nitrogen-containing siloxanes or nitrogen-containing titaniumcompounds, such as trimethoxysilyl propyl ethylene diamine,N-beta(aminoethyl)gamma-aminopropyl trimethoxy silane, isopropyl4-aminobenzene sulfonyl titanate, di(dodecylbenezene sulfonyl)titanate,isopropyl di(4-aminobenzoyl)isostearoyl titanate, isopropyl tri(N-ethylamino)titanate, isopropyl trianthranil titanate, isopropyltri(N,N-dimethyl-ethyl amino)titanate, titanium-4-amino benzenesulfonate oxyacetate, titanium 4-aminobenzoate isostearate oxyacetate,gamma-aminobutyl methyl dimethoxy silane, gamma-aminopropyl methyldimethoxy silane, and gamma-aminopropyl trimethoxy silane, as disclosedin U.S. Pat. Nos. 4,338,387; 4,286,033; and 4,291,110 the disclosures ofwhich are incorporated herein by reference in their entireties.

The blocking layer may be continuous and may have a thickness ranging,for example, from about 0.01 to about 10 micrometers, such as from about0.05 to about 5 micrometers.

The blocking layer 4 may be applied by any suitable technique, such asspraying, dip coating, draw bar coating, gravure coating, silkscreening, air knife coating, reverse roll coating, vacuum deposition,chemical treatment, and the like. For convenience in obtaining thinlayers, the blocking layer may be applied in the form of a dilutesolution, with the solvent being removed after deposition of the coatingby conventional techniques, such as by vacuum, heating, and the like.Generally, a weight ratio of blocking layer material and solvent ofbetween about 0.5:100 to about 30:100, such as about 5:100 to about20:100, is satisfactory for spray and dip coating.

The present disclosure further provides a method for forming theelectrophotographic photoreceptor, in which the charge blocking layer isformed by using a coating solution composed of the grain shapedparticles, the needle shaped particles, the binder resin and an organicsolvent.

The organic solvent may be a mixture of an azeotropic mixture of C₁₋₃lower alcohol and another organic solvent selected from the groupconsisting of dichloromethane, chloroform, 1,2-dichloroethane,1,2-dichloropropane, toluene and tetrahydrofuran. The azeotropic mixturementioned above is a mixture solution in which a composition of theliquid phase and a composition of the vapor phase are coincided witheach other at a certain pressure to give a mixture having a constantboiling point. For example, a mixture consisting of 35 parts by weightof methanol and 65 parts by weight of 1,2-dichloroethane is anazeotropic solution. The presence of an azeotropic composition leads touniform evaporation, thereby forming a uniform charge blocking layerwithout coating defects and improving storage stability of the chargeblocking coating solution.

The binder resin contained in the blocking layer may be formed of thesame materials as that of the blocking layer formed as a single resinlayer. Among them, polyamide resin may be used because it satisfiesvarious conditions required of the binder resin such as (i) polyamideresin is neither dissolved nor swollen in a solution used for formingthe imaging layer on the blocking layer, and (ii) polyamide resin has anexcellent adhesiveness with a conductive support as well as flexibility.In the polyamide resin, alcohol soluble nylon resin may be used, forexample, copolymer nylon polymerized with 6-nylon, 6,6-nylon, 610-nylon,11-nylon, 12-nylon and the like; and nylon which is chemically denaturedsuch as N-alkoxy methyl denatured nylon and N-alkoxy ethyl denaturednylon. Another type of binder resin that may be used is a phenolic resinor polyvinyl butyral resin.

The charge blocking layer is formed by dispersing the binder resin, thegrain shaped particles, and the needle shaped particles in the solventto form a coating solution for the blocking layer; coating theconductive support with the coating solution and drying it. The solventis selected for improving dispersion in the solvent and for preventingthe coating solution from gelation with the elapse of time. Further, theazeotropic solvent may be used for preventing the composition of thecoating solution from being changed as time passes, whereby storagestability of the coating solution may be improved and the coatingsolution may be reproduced.

The phrase “n-type” refers, for example, to materials whichpredominately transport electrons. Typical n-type materials includedibromoanthanthrone, benzimidazole perylene, zinc oxide, titanium oxide,azo compounds such as chlorodiane Blue and bisazo pigments, substituted2,4-dibromotriazines, polynuclear aromatic quinones, zinc sulfide, andthe like.

The phrase “p-type” refers, for example, to materials which transportholes. Typical p-type organic pigments include, for example, metal-freephthalocyanine, titanyl phthalocyanine, gallium phthalocyanine, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, copperphthalocyanine, and the like.

The Adhesive Layer

An intermediate layer 5 between the blocking layer and the chargegenerating layer may, if desired, be provided to promote adhesion.However, in embodiments, a dip coated aluminum drum may be utilizedwithout an adhesive layer.

Additionally, adhesive layers may be provided, if necessary, between anyof the layers in the photoreceptors to ensure adhesion of any adjacentlayers. Alternatively, or in addition, adhesive material may beincorporated into one or both of the respective layers to be adhered.Such optional adhesive layers may have thicknesses of about 0.001micrometer to about 0.2 micrometer. Such an adhesive layer may beapplied, for example, by dissolving adhesive material in an appropriatesolvent, applying by hand, spraying, dip coating, draw bar coating,gravure coating, silk screening, air knife coating, vacuum deposition,chemical treatment, roll coating, wire wound rod coating, and the like,and drying to remove the solvent. Suitable adhesives include, forexample, film-forming polymers, such as polyester, dupont 49,000(available from E. I. duPont de Nemours & Co.), Vitel PE-100 (availablefrom Goodyear Tire and Rubber Co.), polyvinyl butyral, polyvinylpyrrolidone, polyurethane, polymethyl methacrylate, and the like. Theadhesive layer may be composed of a polyester with a M_(w) of from about50,000 to about 100,000, such as about 70,000, and a M_(n) of about35,000.

The Imaging Layer(s)

The imaging layer refers to a layer or layers containing chargegenerating material, charge transport material, or both the chargegenerating material and the charge transport material.

Either a n-type or a p-type charge generating material may be employedin the present photoreceptor.

In the case where the charge generating material and the chargetransport material are in different layers—for example a chargegeneration layer and a charge transport layer—the charge transport layermay comprise a SOF. Further, in the case where the charge generatingmaterial and the charge transport material are in the same layer, thislayer may comprise a SOF.

Charge Generation Layer

Illustrative organic photoconductive charge generating materials includeazo pigments such as Sudan Red, Dian Blue, Janus Green B, and the like;quinone pigments such as Algol Yellow, Pyrene Quinone, IndanthreneBrilliant Violet RRP, and the like; quinocyanine pigments; perylenepigments such as benzimidazole perylene; indigo pigments such as indigo,thioindigo, and the like; bisbenzoimidazole pigments such as IndofastOrange, and the like; phthalocyanine pigments such as copperphthalocyanine, aluminochloro-phthalocyanine, hydroxygalliumphthalocyanine, chlorogallium phthalocyanine, titanyl phthalocyanine andthe like; quinacridone pigments; or azulene compounds. Suitableinorganic photoconductive charge generating materials include forexample cadium sulfide, cadmium sulfoselenide, cadmium selenide,crystalline and amorphous selenium, lead oxide and other chalcogenides.In embodiments, alloys of selenium may be used and include for instanceselenium-arsenic, selenium-tellurium-arsenic, and selenium-tellurium.

Any suitable inactive resin binder material may be employed in thecharge generating layer. Typical organic resinous binders includepolycarbonates, acrylate polymers, methacrylate polymers, vinylpolymers, cellulose polymers, polyesters, polysiloxanes, polyamides,polyurethanes, epoxies, polyvinylacetals, and the like.

To create a dispersion useful as a coating composition, a solvent isused with the charge generating material. The solvent may be for examplecyclohexanone, methyl ethyl ketone, tetrahydrofuran, alkyl acetate, andmixtures thereof. The alkyl acetate (such as butyl acetate and amylacetate) can have from 3 to 5 carbon atoms in the alkyl group. Theamount of solvent in the composition ranges for example from about 70%to about 98% by weight, based on the weight of the composition.

The amount of the charge generating material in the composition rangesfor example from about 0.5% to about 30% by weight, based on the weightof the composition including a solvent. The amount of photoconductiveparticles (i.e, the charge generating material) dispersed in a driedphotoconductive coating varies to some extent with the specificphotoconductive pigment particles selected. For example, whenphthalocyanine organic pigments such as titanyl phthalocyanine andmetal-free phthalocyanine are utilized, satisfactory results areachieved when the dried photoconductive coating comprises between about30 percent by weight and about 90 percent by weight of allphthalocyanine pigments based on the total weight of the driedphotoconductive coating. Because the photoconductive characteristics areaffected by the relative amount of pigment per square centimeter coated,a lower pigment loading may be utilized if the dried photoconductivecoating layer is thicker. Conversely, higher pigment loadings aredesirable where the dried photoconductive layer is to be thinner.

Generally, satisfactory results are achieved with an averagephotoconductive particle size of less than about 0.6 micrometer when thephotoconductive coating is applied by dip coating. The averagephotoconductive particle size may be less than about 0.4 micrometer. Inembodiments, the photoconductive particle size is also less than thethickness of the dried photoconductive coating in which it is dispersed.

In a charge generating layer, the weight ratio of the charge generatingmaterial (“CGM”) to the binder ranges from 30 (CGM):70 (binder) to 70(CGM):30 (binder).

For multilayered photoreceptors comprising a charge generating layer(also referred herein as a photoconductive layer) and a charge transportlayer, satisfactory results may be achieved with a dried photoconductivelayer coating thickness of between about 0.1 micrometer and about 10micrometers. In embodiments, the photoconductive layer thickness isbetween about 0.2 micrometer and about 4 micrometers. However, thesethicknesses also depend upon the pigment loading. Thus, higher pigmentloadings permit the use of thinner photoconductive coatings. Thicknessesoutside these ranges may be selected providing the objectives of thepresent invention are achieved.

Any suitable technique may be utilized to disperse the photoconductiveparticles in the binder and solvent of the coating composition. Typicaldispersion techniques include, for example, ball milling, roll milling,milling in vertical attritors, sand milling, and the like. Typicalmilling times using a ball roll mill is between about 4 and about 6days.

Charge transport materials include an organic polymer, a non-polymericmaterial, or a SOF capable of supporting the injection of photoexcitedholes or transporting electrons from the photoconductive material andallowing the transport of these holes or electrons through the organiclayer to selectively dissipate a surface charge.

Organic Polymer Charge Transport Layer

Illustrative charge transport materials include for example a positivehole transporting material selected from compounds having in the mainchain or the side chain a polycyclic aromatic ring such as anthracene,pyrene, phenanthrene, coronene, and the like, or a nitrogen-containinghetero ring such as indole, carbazole, oxazole, isoxazole, thiazole,imidazole, pyrazole, oxadiazole, pyrazoline, thiadiazole, triazole, andhydrazone compounds. Typical hole transport materials include electrondonor materials, such as carbazole; N-ethyl carbazole; N-isopropylcarbazole; N-phenyl carbazole; tetraphenylpyrene; 1-methyl pyrene;perylene; chrysene; anthracene; tetraphene; 2-phenyl naphthalene;azopyrene; 1-ethyl pyrene; acetyl pyrene; 2,3-benzochrysene;2,4-benzopyrene; 1,4-bromopyrene; poly(N-vinylcarbazole);poly(vinylpyrene); poly(vinyltetraphene); poly(vinyltetracene) andpoly(vinylperylene). Suitable electron transport materials includeelectron acceptors such as 2,4,7-trinitro-9-fluorenone;2,4,5,7-tetranitro-fluorenone; dinitroanthracene; dinitroacridene;tetracyanopyrene; dinitroanthraquinone; andbutylcarbonylfluorenemalononitrile, see U.S. Pat. No. 4,921,769 thedisclosure of which is incorporated herein by reference in its entirety.Other hole transporting materials include arylamines described in U.S.Pat. No. 4,265,990 the disclosure of which is incorporated herein byreference in its entirety, such asN,N′-diphenyl-N,N′-bis(alkylphenyl)-(1,1′-biphenyl)-4,4′-diamine whereinalkyl is selected from the group consisting of methyl, ethyl, propyl,butyl, hexyl, and the like. Other known charge transport layer moleculesmay be selected, reference for example U.S. Pat. Nos. 4,921,773 and4,464,450 the disclosures of which are incorporated herein by referencein their entireties.

Any suitable inactive resin binder may be employed in the chargetransport layer. Typical inactive resin binders soluble in methylenechloride include polycarbonate resin, polyvinylcarbazole, polyester,polyarylate, polystyrene, polyacrylate, polyether, polysulfone, and thelike. Molecular weights can vary from about 20,000 to about 1,500,000.

In a charge transport layer, the weight ratio of the charge transportmaterial (“CTM”) to the binder ranges from 30 (CTM):70 (binder) to 70(CTM):30 (binder).

Any suitable technique may be utilized to apply the charge transportlayer and the charge generating layer to the substrate. Typical coatingtechniques include dip coating, roll coating, spray coating, rotaryatomizers, and the like. The coating techniques may use a wideconcentration of solids. The solids content is between about 2 percentby weight and 30 percent by weight based on the total weight of thedispersion. The expression “solids” refers, for example, to the chargetransport particles and binder components of the charge transportcoating dispersion. These solids concentrations are useful in dipcoating, roll, spray coating, and the like. Generally, a moreconcentrated coating dispersion may be used for roll coating. Drying ofthe deposited coating may be effected by any suitable conventionaltechnique such as oven drying, infra-red radiation drying, air dryingand the like. Generally, the thickness of the transport layer is betweenabout 5 micrometers to about 100 micrometers, but thicknesses outsidethese ranges can also be used. In general, the ratio of the thickness ofthe charge transport layer to the charge generating layer is maintained,for example, from about 2:1 to 200:1 and in some instances as great asabout 400:1.

SOF Charge Transport Layer

Illustrative charge transport SOFs include for example a positive holetransporting material selected from compounds having a segmentcontaining a polycyclic aromatic ring such as anthracene, pyrene,phenanthrene, coronene, and the like, or a nitrogen-containing heteroring such as indole, carbazole, oxazole, isoxazole, thiazole, imidazole,pyrazole, oxadiazole, pyrazoline, thiadiazole, triazole, and hydrazonecompounds. Typical hole transport SOF segments include electron donormaterials, such as carbazole; N-ethyl carbazole; N-isopropyl carbazole;N-phenyl carbazole; tetraphenylpyrene; 1-methyl pyrene; perylene;chrysene; anthracene; tetraphene; 2-phenyl naphthalene; azopyrene;1-ethyl pyrene; acetyl pyrene; 2,3-benzochrysene; 2,4-benzopyrene; and1,4-bromopyrene. Suitable electron transport SOF segments includeelectron acceptors such as 2,4,7-trinitro-9-fluorenone;2,4,5,7-tetranitro-fluorenone; dinitroanthracene; dinitroacridene;tetracyanopyrene; dinitroanthraquinone; andbutylcarbonylfluorenemalononitrile, see U.S. Pat. No. 4,921,769. Otherhole transporting SOF segments include arylamines described in U.S. Pat.No. 4,265,990, such asN,N′-diphenyl-N,N′-bis(alkylphenyl)-(1,1′-biphenyl)-4,4′-diamine whereinalkyl is selected from the group consisting of methyl, ethyl, propyl,butyl, hexyl, and the like. Other known charge transport SOF segmentsmay be selected, reference for example U.S. Pat. Nos. 4,921,773 and4,464,450.

The SOF charge transport layer may be prepared by

-   -   (a) preparing a liquid-containing reaction mixture comprising a        plurality of molecular building blocks with inclined charge        transport properties each comprising a segment and a number of        functional groups;    -   (b) depositing the reaction mixture as a wet film; and    -   (c) promoting a change of the wet film including the molecular        building blocks to a dry film comprising the SOF comprising a        plurality of the segments and a plurality of linkers arranged as        a covalent organic framework, wherein at a macroscopic level the        covalent organic framework is a film.

The deposition of the reaction mixture as a wet layer may be achieved byany suitable conventional technique and applied by any of a number ofapplication methods. Typical application methods include, for example,hand coating, spray coating, web coating, dip coating and the like. TheSOF forming reaction mixture may use a wide range of molecular buildingblock loadings. In embodiments, the loading is between about 2 percentby weight and 50 percent by weight based on the total weight of thereaction mixture. The term “loading” refers, for example, to themolecular building block components of the charge transport SOF reactionmixture. These loadings are useful in dip coating, roll, spray coating,and the like. Generally, a more concentrated coating dispersion may beused for roll coating. Drying of the deposited coating may be affectedby any suitable conventional technique such as oven drying, infra-redradiation drying, air drying and the like. Generally, the thickness ofthe charge transport SOF layer is between about 5 micrometers to about100 micrometers, such as about 10 micrometers to about 70 micrometers or10 micrometers to about 40 micrometers. In general, the ratio of thethickness of the charge transport layer to the charge generating layermay be maintained from about 2:1 to 200:1 and in some instances as greatas 400:1.

Single Layer PIR—Organic Polymer

The materials and procedures described herein may be used to fabricate asingle imaging layer type photoreceptor containing a binder, a chargegenerating material, and a charge transport material. For example, thesolids content in the dispersion for the single imaging layer may rangefrom about 2% to about 30% by weight, based on the weight of thedispersion.

Where the imaging layer is a single layer combining the functions of thecharge generating layer and the charge transport layer, illustrativeamounts of the components contained therein are as follows: chargegenerating material (about 5% to about 40% by weight), charge transportmaterial (about 20% to about 60% by weight), and binder (the balance ofthe imaging layer).

Single Layer PIR—SOF

The materials and procedures described herein may be used to fabricate asingle imaging layer type photoreceptor containing a charge generatingmaterial and a charge transport SOF. For example, the solids content inthe dispersion for the single imaging layer may range from about 2% toabout 30% by weight, based on the weight of the dispersion.

Where the imaging layer is a single layer combining the functions of thecharge generating layer and the charge transport layer, illustrativeamounts of the components contained therein are as follows: chargegenerating material (about 2% to about 40% by weight), with an inclinedadded functionality of charge transport molecular building block (about20% to about 75% by weight).

The Overcoating Layer

Embodiments in accordance with the present disclosure can, optionally,further include an overcoating layer or layers 8, which, if employed,are positioned over the charge generation layer or over the chargetransport layer. This layer comprises SOFs that are electricallyinsulating or slightly semi-conductive.

Such a protective overcoating layer includes a SOF forming reactionmixture containing a plurality of molecular building blocks thatoptionally contain charge transport segments.

Additives may be present in the overcoating layer in the range of about0.5 to about 40 weight percent of the overcoating layer. In embodiments,additives include organic and inorganic particles which can furtherimprove the wear resistance and/or provide charge relaxation property.In embodiments, organic particles include Teflon powder, carbon black,and graphite particles. In embodiments, inorganic particles includeinsulating and semiconducting metal oxide particles such as silica, zincoxide, tin oxide and the like. Another semiconducting additive is theoxidized oligomer salts as described in U.S. Pat. No. 5,853,906 thedisclosure of which is incorporated herein by reference in its entirety.In embodiments, oligomer salts are oxidizedN,N,N′,N′-tetra-p-tolyl-4,4′-biphenyldiamine salt.

The SOF overcoating layer may be prepared by

-   -   (a) preparing a liquid-containing reaction mixture comprising a        plurality of molecular building blocks with an inclined charge        transport properties each comprising a segment and a number of        functional groups;    -   (b) depositing the reaction mixture as a wet film; and    -   (c) promoting a change of the wet film including the molecular        building blocks to a dry film comprising the SOF comprising a        plurality of the segments and a plurality of linkers arranged as        a covalent organic framework, wherein at a macroscopic level the        covalent organic framework is a film.

The deposition of the reaction mixture as a wet layer may be achieved byany suitable conventional technique and applied by any of a number ofapplication methods. Typical application methods include, for example,hand coating, spray coating, web coating, dip coating and the like.Promoting the change of the wet film to the dry SOF may be affected byany suitable conventional techniques, such as oven drying, infraredradiation drying, air drying, and the like.

Overcoating layers from about 2 micrometers to about 15 micrometers,such as from about 3 micrometers to about 8 micrometers are effective inpreventing charge transport molecule leaching, crystallization, andcharge transport layer cracking in addition to providing scratch andwear resistance.

The Ground Strip

The ground strip 9 may comprise a film-forming binder and electricallyconductive particles. Cellulose may be used to disperse the conductiveparticles. Any suitable electrically conductive particles may be used inthe electrically conductive ground strip layer 8. The ground strip 8may, for example, comprise materials that include those enumerated inU.S. Pat. No. 4,664,995 the disclosure of which is incorporated hereinby reference in its entirety. Typical electrically conductive particlesinclude, for example, carbon black, graphite, copper, silver, gold,nickel, tantalum, chromium, zirconium, vanadium, niobium, indium tinoxide, and the like.

The electrically conductive particles may have any suitable shape.Typical shapes include irregular, granular, spherical, elliptical,cubic, flake, filament, and the like. In embodiments, the electricallyconductive particles should have a particle size less than the thicknessof the electrically conductive ground strip layer to avoid anelectrically conductive ground strip layer having an excessivelyirregular outer surface. An average particle size of less than about 10micrometers generally avoids excessive protrusion of the electricallyconductive particles at the outer surface of the dried ground striplayer and ensures relatively uniform dispersion of the particles throughthe matrix of the dried ground strip layer. Concentration of theconductive particles to be used in the ground strip depends on factorssuch as the conductivity of the specific conductive materials utilized.

In embodiments, the ground strip layer may have a thickness of fromabout 7 micrometers to about 42 micrometers, such as from about 14micrometers to about 27 micrometers.

Application B: SOFs in Thin Film Transistors

FIG. 4 schematically illustrates a thin film transistor (TFT)configuration 30 comprised of a substrate 36, a gate electrode 38, asource electrode 40 and a drain electrode 42, an insulating layer 34,and an organic semiconductor layer 32.

The substrate may be composed of for instance silicon wafer, glassplate, metal sheet, plastic film or sheet. For structurally flexibledevices, plastic substrate, such as for example polyester,polycarbonate, polyimide sheets and the like may be used. The thicknessof the substrate may be from amount 10 micrometers to over 10millimeters with an exemplary thickness being from about 50 micrometersto about 2 millimeters, especially for a flexible plastic substrate andfrom about 0.4 to about 10 millimeters for a rigid substrate such asglass or silicon.

The compositions of the gate electrode, the source electrode, and thedrain electrode are now discussed. The gate electrode may be a thinmetal film, a conducting polymer film, a conducting film made fromconducting ink or paste or the substrate itself, for example heavilydoped silicon. Examples of gate electrode materials include, forexample, aluminum, silver, gold, chromium, indium tin oxide, conductingpolymers such as polystyrene sulfonate-dopedpoly(3,4-ethylenedioxythiophene) (PSS-PEDOT), conducting ink/pastecomprised of carbon black/graphite or colloidal silver dispersion inpolymer binders, such as ELECTRODAG™ available from Acheson ColloidsCompany. The gate electrode layer may be prepared by vacuum evaporation,sputtering of metals or conductive metal oxides, coating from conductingpolymer solutions or conducting inks by spin coating, casting orprinting. The thickness of the gate electrode layer ranges, for example,from about 10 to about 200 nanometers for metal films and in the rangeof about 1 to about 10 micrometers for polymer conductors. The sourceand drain electrode layers may be fabricated from materials whichprovide a low resistance ohmic contact to the semiconductor layer.Typical materials suitable for use as source and drain electrodesinclude those of the gate electrode materials such as silver, gold,nickel, aluminum, platinum, conducting polymers and conducting inks.Typical thicknesses of source and drain electrodes are about, forexample, from about 40 nanometers to about 1 micrometer, such as about100 to about 400 nanometers.

The insulating layer generally may be an inorganic material film or anorganic polymer film. Inorganic materials suitable as the insulatinglayer include, for example, silicon oxide, silicon nitride, aluminumoxide, barium titanate, barium zirconium titanate and the like; examplesof organic polymers for the insulating layer include polyesters,polycarbonates, poly(vinyl phenol), polyimides, polystyrene,poly(methacrylate)s, poly(acrylate)s, epoxy resin, liquid glass, and thelike. The thickness of the insulating layer is, for example from about10 nanometers to about 500 nanometers depending on the dielectricconstant of the dielectric material used. An exemplary thickness of theinsulating layer is from about 100 nanometers to about 500 nanometers,such as from about 200 nanometers to about 400 nanometers. Theinsulating layer may have a conductivity that is for example less thanabout 10⁻¹² S/cm.

Situated, for example, between and in contact with the insulating layerand the source/drain electrodes is the semiconductor layer wherein thethickness of the semiconductor layer is generally, for example, about 10nanometers to about 1 micrometer, or about 40 to about 100 nanometers.The semiconductor layer may comprise a SOF with semiconductor addedfunctionality. The process for preparing the SOF with semiconductoradded functionality is as follows:

-   (a) preparing a liquid-containing reaction mixture comprising a    plurality of molecular building blocks each comprising a segment    with inclined semiconductor properties and a number of functional    groups;-   (b) depositing the reaction mixture as a wet film; and-   (c) promoting a change of the wet film including the molecular    building blocks to a dry film comprising the SOF comprising a    plurality of the segments and a plurality of linkers arranged as a    covalent organic framework, wherein at a macroscopic level the    covalent organic framework is a film which is multi-segment thick.

The insulating layer, the gate electrode, the semiconductor layer, thesource electrode, and the drain electrode are formed in any sequence,particularly where in embodiments the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconductor layer.The phrase “in any sequence” includes sequential and simultaneousformation. For example, the source electrode and the drain electrode maybe formed simultaneously or sequentially. The composition, fabrication,and operation of thin film transistors are described in Bao et al., U.S.Pat. No. 6,107,117, the disclosure of which is totally incorporatedherein by reference.

Examples

A number of examples of the process used to make SOFs are set forthherein and are illustrative of the different compositions, conditions,techniques that may be utilized. Identified within each example are thenominal actions associated with this activity. The sequence and numberof actions along with operational parameters, such as temperature, time,coating method, and the like, are not limited by the following examples.All proportions are by weight unless otherwise indicated. The term “rt”refers, for example, to temperatures ranging from about 20° C. to about25° C. Mechanical measurements were measured on a TA Instruments DMAQ800 dynamic mechanical analyzer using methods standard in the art.Differential scanning calorimetery was measured on a TA Instruments DSC2910 differential scanning calorimeter using methods standard in theart. Thermal gravimetric analysis was measured on a TA Instruments TGA2950 thermal gravimetric analyzer using methods standard in the art.FT-IR spectra was measured on a Nicolet Magna 550 spectrometer usingmethods standard in the art. Thickness measurements<1 micron weremeasured on a Dektak 6 m Surface Profiler. Surface energies weremeasured on a Fibro DAT 1100 (Sweden) contact angle instrument usingmethods standard in the art. Unless otherwise noted, the SOFs producedin the following examples were either defect-free SOFs or substantiallydefect-free SOFs.

The SOFs coated onto Mylar were delaminated by immersion in a roomtemperature water bath. After soaking for 10 minutes the SOF filmgenerally detached from Mylar substrate. This process is most efficientwith a SOF coated onto substrates known to have high surface energy(polar), such as glass, mica, salt, and the like.

Given the examples below it will be apparent, that the compositionsprepared by the methods of the present disclosure may be practiced withmany types of components and may have many different uses in accordancewith the disclosure above and as pointed out hereinafter.

Embodiment of a Patterned SOF Composition

An embodiment of the disclosure is to attain a SOF wherein themicroscopic arrangement of segments is patterned. The term “patterning”refers, for example, to the sequence in which segments are linkedtogether. A patterned SOF would therefore embody a composition wherein,for example, segment A is only connected to segment B, and conversely,segment B is only connected to segment A. Further, a system wherein onlyone segment exists, say segment A, is employed is will be patternedbecause A is intended to only react with A. In principle a patterned SOFmay be achieved using any number of segment types. The patterning ofsegments may be controlled by using molecular building blocks whosefunctional group reactivity is intended to compliment a partnermolecular building block and wherein the likelihood of a molecularbuilding block to react with itself is minimized. The aforementionedstrategy to segment patterning is non-limiting. Instances where aspecific strategy to control patterning has not been deliberatelyimplemented are also embodied herein.

A patterned film may be detected using spectroscopic techniques that arecapable of assessing the successful formation of linking groups in aSOF. Such spectroscopies include, for example, Fourier-transfer infraredspectroscopy, Raman spectroscopy, and solid-state nuclear magneticresonance spectroscopy. Upon acquiring a data by a spectroscopictechnique from a sample, the absence of signals from functional groupson building blocks and the emergence of signals from linking groupsindicate the reaction between building blocks and the concomitantpatterning and formation of an SOF.

Different degrees of patterning are also embodied. Full patterning of aSOF will be detected by the complete absence of spectroscopic signalsfrom building block functional groups. Also embodied are SOFs havinglowered degrees of patterning wherein domains of patterning exist withinthe SOF. SOFs with domains of patterning, when measuredspectroscopically, will produce signals from building block functionalgroups which remain unmodified at the periphery of a patterned domain.

It is appreciated that a very low degree of patterning is associatedwith inefficient reaction between building blocks and the inability toform a film. Therefore, successful implementation of the process of thepresent disclosure requires appreciable patterning between buildingblocks within the SOF. The degree of necessary patterning to form a SOFis variable and can depend on the chosen building blocks and desiredlinking groups. The minimum degree of patterning required is thatrequired to form a film using the process described herein, and may bequantified as formation of about 20% or more of the intended linkinggroups, such as about 40% or more of the intended linking groups orabout 50% or more of the intended linking groups; the nominal degree ofpatterning embodied by the present disclosure is formation of about 60%of the intended linking group, such as formation of about 100% of theintended linking groups. Formation of linking groups may be detectedspectroscopically as described earlier in the embodiments.

Production of a Patterned SOF

The following experiments demonstrate the development of a patternedSOF. The activity described below is non-limiting as it will be apparentthat many types of approaches may be used to generate patterning in aSOF.

EXAMPLE 1 describes the synthesis of a Type 2 SOF wherein components arecombined such that etherification linking chemistry is promoted betweentwo building blocks. The presence of an acid catalyst and a heatingaction yield a SOF with the method described in EXAMPLE 1.

Example 1 Type 2 SOF

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block benzene-1,4-dimethanol[segment=p-xylyl; Fg=hydroxyl (—OH); (0.47 g, 3.4 mmol)] and a secondbuilding blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.12 g, 1.7 mmol)], and 17.9 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.31 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Promotion of the change of the wet film to a dry SOF. Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided a SOF having a thickness rangingfrom about 3-6 microns, which may be delaminated from the substrate as asingle free-standing SOF. The color of the SOF was green. TheFourier-transform infrared spectrum of a portion of this SOF is providedin FIG. 5.

To demonstrate that the SOF prepared in EXAMPLE 1 comprises segmentsfrom the employed molecular building blocks that are patterned withinthe SOF, three control experiments were conducted. Namely, three liquidreaction mixtures were prepared using the same procedure as set forth inAction A in EXAMPLE 1; however, each of these three formulations weremodified as follows:

-   -   (Control reaction mixture 1; Example 2) the building block        benzene-1,4-dimethanol was not included.    -   (Control reaction mixture 2; Example 3) the building block        N4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine        was not included.    -   (Control reaction mixture 3; Example 4) the catalyst        p-toluenesulfonic acid was not included

The full descriptions of the SOF forming process for the above describedcontrol experiments are detailed in EXAMPLES 2-4 below.

Example 2 Control Experiment Wherein the Building BlockBenzene-1,4-dimethanol was Not Included

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.12 g, 1.7 mmol)], and 17.9 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.31 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Attempted promotion of the change of the wet film to a drySOF. The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions did not provide a film. Instead, aprecipitated powder of the building block was deposited onto thesubstrate.

Example 3 Control Experiment Wherein the Building BlockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine wasnot included

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block benzene-1,4-dimethanol[segment=p-xylyl; Fg=hydroxyl (—OH); (0.47 g, 3.4 mmol)] and 17.9 g of1-methoxy-2-propanol. The mixture was shaken and heated to 60° C. untila homogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.31 g of a 10wt % solution of p-toluenesulfonic acid in 1-methoxy-2-propanol to yieldthe liquid containing reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Attempted promotion of the change of the wet film to a drySOF. The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions did not provide a film Instead, aprecipitated powder of the building block was deposited onto thesubstrate.

Example 4 Control Experiment wherein the Acid Catalyst p-toluenesulfonicAcid was not Included

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block benzene-1,4-dimethanol[segment=p-xylyl; Fg=hydroxyl (—OH); (0.47 g, 3.4 mmol)] and a secondbuilding blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.12 g, 1.7 mmol)], and 17.9 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane to yield the liquid containingreaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap.

(Action C) Attempted promotion of the change of the wet film to a drySOF. The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions did not provide a film. Instead, aprecipitated powder of the building blocks was deposited onto thesubstrate.

As described in EXAMPLES 2-4, each of the three control reactionmixtures were subjected to Action B and Action C as outlined inEXAMPLE 1. However, in all cases a SOF did not form; the building blockssimply precipitated on the substrate. It is concluded from these resultsthat building blocks cannot react with themselves under the statedprocessing conditions nor can the building blocks react in the absenceof a promoter (p-toluenesulfonic acid). Therefore, the activitydescribed in EXAMPLE 1 is one wherein building blocks(benzene-1,4-dimethanol andN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine)can only react with each other when promoted to do so. A patterned SOFresults when the segments p-xylyl andN4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine connect only with eachother. The Fourier-transform infrared spectrum, compared to that of theproducts of the control experiments (FIG. 6) of the SOF shows absence offunctional groups (notably the absence of the hydroxyl band from thebenzene-1,4-dimthanol) from the starting materials and further supportsthat the connectivity between segments has proceed as described above.Also, the complete absence of the hydroxyl band in the spectrum for theSOF indicates that the patterning is to a very high degree.

Described below are further Examples of defect-free SOFs and/orsubstantially defect-free SOFs prepared in accordance with the presentdisclosure. In the following examples (Action A) is the preparation ofthe liquid containing reaction mixture; (Action B) is the deposition ofreaction mixture as a wet film; and (Action C) is the promotion of thechange of the wet film to a dry SOF.

Example 5 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,3,5-trimethanol [segment=benzene-1,3,5-trimethyl; Fg=hydroxyl(—OH); (0.2 g, 1.2 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.59 g, 0.8 mmol)], and 8.95 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.16 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the reflective side of a metalized (TiZr) MYLAR™ substrate using aconstant velocity draw down coater outfitted with a bird bar having an20 mil gap. (Action C) The metalized MYLAR™ substrate supporting the wetlayer was rapidly transferred to an actively vented oven preheated to130° C. and left to heat for 40 min. These actions provided a SOF havinga thickness ranging from about 2-4 microns that could be delaminatedfrom the substrate as a single free-standing SOF. The color of the SOFwas green.

Example 6 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.21 g, 1.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.58 g, 0.87 mmol)], and 8.95 g of 1-methoxy-2-propanol.The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.16 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the reflective side of a metalized (TiZr) MYLAR™ substrate using aconstant velocity draw down coater outfitted with a bird bar having a 20mil gap. (Action C) The metalized MYLAR™ substrate supporting the wetlayer was rapidly transferred to an actively vented oven preheated to130° C. and left to heat for 40 min. These actions provided a SOF havinga thickness ranging from about 4-5 microns that could be delaminatedfrom the substrate as a single free standing SOF. The color of the SOFwas green. The Fourier-transform infrared spectrum of a portion of thisSOF is provided in FIG. 7.

Example 7 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (—OH); (0.64 g, 4.6mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.54 g, 2.3 mmol)], and 7.51 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted, which was then filtered through a 0.45 micron PTFE membrane.To the filtered solution was added an acid catalyst delivered as 0.28 gof a 10 wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yieldthe liquid containing reaction mixture. (Action B) The reaction mixturewas applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 4 min. These actionsprovided a SOF having a thickness ranging from about 8-12 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was green.

Example 8 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.57 g, 4.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.61 g, 2.42 mmol)], and 7.51 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to rt, the solution was filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.22 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided a SOF having a thickness rangingfrom about 12-20 microns that could be delaminated from the substrate asa single free-standing film. The color of the SOF was green.

Example 9 Type 2 SOF

(Action A) The following were combined: the building block4,4′-(cyclohexane-1,1-diyl)diphenol[segment=4,4′-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (—OH); (0.97g, 6 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.21 g, 1.8 mmol)], and 7.51 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to rt, the solution was filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.22 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided a SOF having a thickness rangingfrom about 12-20 microns that could be delaminated from the substrate asa single free-standing film. The color of the SOF was green. TheFourier-transform infrared spectrum of SOF is provided in FIG. 8.

Example 10 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (—OH); (0.52 g, 3.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.26 g, 1.9 mmol)], and 6.3 g of 1,4-dioxane and 1.57 gof n-butyl acetate. The mixture was shaken and heated to 60° C. until ahomogenous solution resulted, which was then filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.28 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having an 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 4 min. These actions provided a SOF having a thickness of 7-10microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was green.

Example 11 Type 2 SOF

(Action A) Same as EXAMPLE 7. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 20 min.These actions provided a uniformly coated multilayer device wherein theSOF had a thickness ranging from about 9-10 microns.

Example 12 Type 2 SOF

(Action A) The following were combined: the building blockbenzene-1,4-dimethanol [segment=p-xylyl; Fg=hydroxyl (—OH); (0.52 g, 3.8mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.26 g, 1.9 mmol)], and 6.3 g of 1,4-dioxane and 1.57 gof methyl isobutyl ketone. The mixture was shaken and heated to 60° C.until a homogenous solution resulted, which was then filtered through a0.45 micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.28 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having an 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 4 min. These actions provided a SOF having a thickness rangingfrom about 7-10 microns that could be delaminated from substrate as asingle free-standing film. The color of the SOF was green.

Example 13 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.47 g, 4.0mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.31 g, 2.0 mmol)], 6.3 g of 1,4-dioxane, and 1.57 g ofn-butyl acetate. The mixture was shaken and heated to 60° C. until ahomogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.22 g of a 10wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yield theliquid containing reaction mixture. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 40 min. These actionsprovided a SOF having a thickness ranging from about 8-12 microns thatcould be delaminated from the substrate as a single free-standing film.The color of the SOF was green.

Example 14 Type 2 SOF

(Action A) Same as EXAMPLE 10. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 20 min.These actions provided a uniformly coated multilayer device wherein theSOF had a thickness ranging from about 9-10 microns.

Example 15 Type 2 SOF

(Action A) The following were combined: the building block1,6-n-hexanediol [segment=n-hexyl; Fg=hydroxyl (—OH); (0.47 g, 4.0mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (1.31 g, 2.0 mmol)], 6.3 g of 1,4-dioxane, and 1.57 g ofmethyl isobutyl ketone.

The mixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.22 g of a 10 wt % solution ofp-toluenesulfonic acid in 1,4-dioxane to yield the liquid containingreaction mixture. (Action B) The reaction mixture was applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer wasrapidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 40 min. These actions provided a SOF having a thicknessranging from about 8-12 microns that could be delaminated from thesubstrate as a single free-standing film The color of the SOF was green.

Example 16 Type 2 SOF

(Action A) The following were combined: the building block4,4′-(cyclohexane-1,1-diyl)diphenol[segment=4,4′-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (—OH); (0.8 g,(Action C)0 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.8 g, 1.5 mmol)], 1,4-dioxane, and 1.57 g of n-butylacetate. The mixture was shaken and heated to 60° C. until a homogenoussolution resulted. Upon cooling to rt, the solution was filtered througha 0.45 micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.22 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 10 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided SOF having a thickness of about12 microns that could be delaminated from the substrate as a singlefree-standing film. The color of the SOF was green.

Example 17 Type 2 SOF

(Action A) Same as EXAMPLE 13. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 20 min.These actions provided a uniformly coated multilayer device wherein theSOF had a thickness ranging from about 9-10 microns.

Example 18 Type 2 SOF

(Action A) The following were combined: the building block4,4′-(cyclohexane-1,1-diyl)diphenol[segment=4,4′-(cyclohexane-1,1-diyl)diphenyl; Fg=hydroxyl (—OH); (0.8 g,3.0 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.8 g, 1.5 mmol)], 1,4-dioxane, and 1.57 g of methylisobutyl ketone. The mixture was shaken and heated to 60° C. until ahomogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.22 g of a 10wt % solution of p-toluenesulfonic acid in 1,4-dioxane to yield theliquid containing reaction mixture. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 130° C. and left to heat for 40 min. These actionsprovided SOF having a thickness of about 12 microns that could bedelaminated from the substrate as a single free-standing film. The colorof the SOF was green.

Example 19 Type 2 SOF

(Action A) Same as EXAMPLE 7. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was allowed to dry at ambienttemperature in an actively vented fume hood for 5 min and was thentransferred to an actively vented oven preheated to 120° C. and left toheat for 15 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness ranging from about 9-10 microns.

Example 20 Type 2 SOF

(Action A) Same as EXAMPLE 10. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was allowed to dry at ambienttemperature in an actively vented fume hood for 5 min and was thentransferred to an actively vented oven preheated to 120° C. and left toheat for 15 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness ranging from about 9-10 microns.

Example 21 Type 2 SOF

(Action A) Same as EXAMPLE 13. (Action B) The reaction mixture wasapplied to a photoconductive layer, containing a pigment and polymericbinder, supported on metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 10 mil gap.(Action C) The supported wet layer was allowed to dry at ambienttemperature in an actively vented fume hood for 5 min and was thentransferred to an actively vented oven preheated to 120° C. and left toheat for 15 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness ranging from about 9-10 micronsand could not be delaminated.

Example 22 Type 2 SOF

(Action A) Same as EXAMPLE 7. (Action B) The reaction mixture wasapplied to a layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 10 mil gap. (Action C) The supported wet layerwas allowed to dry at ambient temperature in an actively vented fumehood for 5 min and was then transferred to an actively vented ovenpreheated to 120° C. and left to heat for 15 min. These actions provideda uniformly coated multilayer device wherein the SOF had a thicknessranging from about 9-10 microns.

Example 23 Type 2 SOF

(Action A) Same as EXAMPLE 10. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 10 mil gap. (Action C) The supported wet layerwas allowed to dry at ambient temperature in an actively vented fumehood for 5 min and was then transferred to an actively vented ovenpreheated to 120° C. and left to heat for 15 min. These actions provideda uniformly coated multilayer device wherein the SOF had a thicknessranging from about 9-10 microns.

Example 24 Type 2 SOF

(Action A) Same as EXAMPLE 13. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 10 mil gap. (Action C) The supported wet layerwas allowed to dry at ambient temperature in an actively vented fumehood for 5 min and was then transferred to an actively vented ovenpreheated to 120° C. and left to heat for 15 min. These actions provideda uniformly coated multilayer device wherein the SOF had a thicknessranging from about 9-10 microns.

Example 25 Type 1 SOF

(Action A) The following were combined: the building block(4,4′,4″,4′″-(biphenyl-4,4′-diylbis(azanetriyl))tetrakis(benzene-4,1-diyl))tetramethanol[segment=(4,4′,4″,4′″-(biphenyl-4,4′-diylbis(azanetriyl))tetrakis(benzene-4,1-diyl);Fg=alcohol (—OH); (1.48 g, 2.4 mmol)], and 8.3 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.15 g of a 10 wt % solution ofp-toluenesulfonic acid in 1,4-dioxane to yield the liquid containingreaction mixture. (Action B) The reaction mixture was applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 25 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer wasrapidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 40 min These actions provided SOF having a thicknessranging from about 8-24 microns. The color of the SOF was green.

Example 26 Type 1 SOF

(Action A) The following were combined: the building4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethanol[segment=(4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethyl); Fg=alcohol(—OH); (1.48 g, 4.4 mmol)], and 8.3 g of 1,4-dioxane. The mixture wasshaken and heated to 60° C. until a homogenous solution resulted. Uponcooling to room temperature, the solution was filtered through a 0.45micron PTFE membrane. To the filtered solution was added an acidcatalyst delivered as 0.15 g of a 10 wt % solution of p-toluenesulfonicacid in 1,4-dioxane to yield the liquid containing reaction mixture.(Action B) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 15 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 130° C. and left toheat for 40 min. These actions provided SOF having a thickness rangingfrom about 6-15 microns that could be delaminated from substrate as asingle free-standing film. The color of the SOF was green. TheFourier-transform infrared spectrum of this film is provided in FIG. 9.Two-dimensional X-ray scattering data is provided in FIG. 15. As seen inFIG. 15, no signal above the background is present, indicating theabsence of molecular order having any detectable periodicity.

Example 27 Type 2 SOF

(Action A) The following were combined: the building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.26 g, 0.40 mmol)] and a second building block3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropan-1-ol[segment=3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropyl;Fg=hydroxy (—OH); (0.34 g, 0.78 mmol)], and 1.29 mL of1-methoxy-2-propanol. The mixture was shaken and heated to 60° C. untila homogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. To thefiltered solution was added an acid catalyst delivered as 0.2 g of a 10wt % solution of p-toluenesulfonic acid in 1-methoxy-2-propanol to yieldthe liquid containing reaction mixture. (Action B) The reaction mixturewas applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having an 8 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 150° C. and left to heat for 40 min. These actionsprovided SOF having a thickness ranging from about 15-20 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was green.

Example 28 Type 2 SOF

(Action A) Same as EXAMPLE 24. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder using a constant velocity draw down coater outfittedwith a bird bar having a 5 mil gap. (Action C) The supported wet layerwas rapidly transferred to an actively vented oven preheated to 130° C.and left to heat for 40 min. These actions provided a uniformly coatedmultilayer device wherein the SOF had a thickness of about 5 microns.

Example 29 Type 2 SOF

(Action A) Same as EXAMPLE 24. (Action B) The reaction mixture wasapplied to layered photosensitive member comprising a generator layerand a transport layer containing a diamine type molecule dispersed in apolymeric binder affixed to a spin coating device rotating at 750 rpm.The liquid reaction mixture was dropped at the centre rotating substrateto deposit the wet layer. (Action C) The supported wet layer was rapidlytransferred to an actively vented oven preheated to 140° C. and left toheat for 40 min. These actions provided a uniformly coated multilayerdevice wherein the SOF had a thickness of about 0.2 microns.

Example 30 Type 2 SOF

(Action A) The following were combined: the building blockterephthalaldehyde [segment=benzene; Fg=aldehyde (—CHO); (0.18 g, 1.3mmol)] and a second building block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (0.26 g, 0.89 mmol)], and 2.5g of tetrahydrofuran. The mixture was shaken until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.045 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-tetrahydrofuran to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the reflective side of a metalized (TiZr) MYLAR™ substrate using aconstant velocity draw down coater outfitted with a bird bar having an 5mil gap. (Action C) The metalized MYLAR™ substrate supporting the wetlayer was rapidly transferred to an actively vented oven preheated to120° C. and left to heat for 40 min These actions provided a SOF havinga thickness of about 6 microns that could be delaminated from substrateas a single free-standing film. The color of the SOF was red-orange. TheFourier-transform infrared spectrum of this film is provided in FIG. 10.

Example 31 Type 1 SOF

(Action A) The following were combined: the building block4,4′,4″-nitrilotribenzaldehyde [segment=triphenylamine; Fg=aldehyde(—CHO); (0.16 g, 0.4 mmol)] and a second building blocktris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (0.14g, 0.4 mmol)], and 1.9 g of tetrahydrofuran. The mixture was stirreduntil a homogenous solution resulted. Upon cooling to room temperature,the solution was filtered through a 0.45 micron PTFE membrane. (ActionB) The reaction mixture was applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having an 5 mil gap. (Action C) Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 120° C. and left toheat for 40 min. These actions provided a SOF having a thickness ofabout 6 microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was red. The Fourier-transforminfrared spectrum of this film is provided in FIG. 11.

Example 32 Type 2 SOF

(Action A) The following were combined: the building block glyoxal[segment=single covalent bond; Fg=aldehyde (—CHO); (0.31 g, 5.8mmol—added as 40 wt % solution in water i.e. 0.77 g aqueous glyoxal)]and a second building block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (1.14 g, (3.9 mmol)], and 8.27g of tetrahydrofuran. The mixture was shaken until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. (Action B) The reaction mixture wasapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 10 mil gap. (Action C) The metalized MYLAR™ substratesupporting the wet layer was rapidly transferred to an actively ventedoven preheated to 120° C. and left to heat for 40 min. These actionsprovided a SOF having a thickness ranging from about 6-12 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was red.

Example 33 Type 2 SOF

(Action A) The following were combined: the building blockterephthalaldehyde [segment=benzene; Fg=aldehyde (—CHO); (0.18 g, 1.3mmol)] and a second building block tris(4-aminophenyl)amine[segment=triphenylamine; Fg=amine (—NH₂); (0.26 g, 0.89 mmol)], 2.5 g oftetrahydrofuran, and 0.4 g water. The mixture was shaken until ahomogenous solution resulted. Upon cooling to room temperature, thesolution was filtered through a 0.45 micron PTFE membrane. (Action B)The reaction mixture was applied to the reflective side of a metalized(TiZr) MYLAR™ substrate using a constant velocity draw down coateroutfitted with a bird bar having a 5 mil gap. (Action C) The metalizedMYLAR™ substrate supporting the wet layer was rapidly transferred to anactively vented oven preheated to 120° C. and left to heat for 40 min.These actions provided a SOF having a thickness ranging 6 microns thatcould be delaminated from substrate as a single free-standing film. Thecolor of the SOF was red-orange.

Example 34 Type 1 SOF

(Action A) The following were combined: the building block4,4′,4″-nitrilotribenzaldehyde [segment=triphenylamine; Fg=aldehyde(—CHO); (0.16 g, 0.4 mmol)] and a second building blocktris(4-aminophenyl)amine [segment=triphenylamine; Fg=amine (—NH₂); (0.14g, 0.4 mmol)], 1.9 g of tetrahydrofuran, and 0.4 g water. The mixturewas stirred until a homogenous solution resulted. Upon cooling to roomtemperature, the solution was filtered through a 0.45 micron PTFEmembrane. (Action B) The reaction mixture was applied to the reflectiveside of a metalized (TiZr) MYLAR™ substrate using a constant velocitydraw down coater outfitted with a bird bar having an 5 mil gap. (ActionC) The metalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 120° C. and left toheat for 40 min. These actions provided a SOF having a thickness ofabout 6 microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was red-orange.

Example 35 Type 2 SOF

(Action A) Same as EXAMPLE 28. (Action B) The reaction mixture wasdropped from a glass pipette onto a glass slide. (Action C) The glassslide was heated to 80° C. on a heating stage yielding a deep red SOFhaving a thickness of about 200 microns which could be delaminated fromthe glass slide.

Example 36 Type 1 SOF

(Action A) The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 5.12 g]; the additives Cymel303 (55 mg) and Silclean3700 (210 mg), and the catalyst Nacure XP-357 (267 mg) and1-methoxy-2-propanol (13.27 g). The mixture was mixed on a rolling waverotator for 10 min and then heated at 55° C. for 65 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. (Action B) The reaction mixture was applied to acommercially available, 30 mm drum photoreceptor using a cup coater(Tsukiage coating) at a pull-rate of 240 mm/min. (Action C) Thephotoreceptor drum supporting the wet layer was rapidly transferred toan actively vented oven preheated to 140° C. and left to heat for 40min. These actions provided a SOF having a thickness of about 6.9microns. FIG. 12 is a photo-induced discharge curve (PIDC) illustratingthe photoconductivity of this SOF overcoat layer (voltage at 75 ms(expose-to-measure)).

Example 37 Type 1 SOF with Additives

(Action A) The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 4.65 g]; the additives Cymel303 (49 mg) and Silclean3700 (205 mg), and the catalyst Nacure XP-357 (254 mg) and1-methoxy-2-propanol (12.25 g). The mixture was mixed on a rolling waverotator for 10 min and then heated at 55° C. for 65 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. A polyethylene wax dispersion (average particle size=5.5microns, 40% solids in i-propyl alcohol, 613 mg) was added to thereaction mixture which was sonicated for 10 min and mixed on the rotatorfor 30 min. (Action B) The reaction mixture was applied to acommercially available, 30 mm drum photoreceptor using a cup coater(Tsukiage coating) at a pull-rate of 240 mm/min. (Action C) Thephotoreceptor drum supporting the wet layer was rapidly transferred toan actively vented oven preheated to 140° C. and left to heat for 40min. These actions provided a film having a thickness of 6.9 micronswith even incorporation of the wax particles in the SOF. FIG. 13 is aphoto-induced discharge curve (PIDC) illustrating the photoconductivityof this SOF overcoat layer (voltage at 75 ms (expose-to-measure)).

Example 38 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 3.36 g] and the building blockN,N′-diphenyl-N,N′-bis-(3-hydroxyphenyl)-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetraphenyl-biphenyl-4,4′-diamine; Fg=hydroxyl (—OH);5.56 g]; the additives Cymel303 (480 mg) and Silclean 3700 (383 mg), andthe catalyst Nacure XP-357 (480 mg) and 1-methoxy-2-propanol (33.24 g).The mixture was mixed on a rolling wave rotator for 10 min and thenheated at 55° C. for 65 min until a homogenous solution resulted. Themixture was placed on the rotator and cooled to room temperature. Thesolution was filtered through a 1 micron PTFE membrane. (Action B) Thereaction mixture was applied to a commercially available, 30 mm drumphotoreceptor using a cup coater (Tsukiage coating) at a pull-rate of485 mm/min. (Action C) The photoreceptor drum supporting the wet layerwas rapidly transferred to an actively vented oven preheated to 140° C.and left to heat for 40 min. These actions provided a film having athickness ranging from 6.0 to 6.2 microns. FIG. 14 is a photo-induceddischarge curve (PIDC) illustrating the photoconductivity of this SOFovercoat layer (voltage at 75 ms (expose-to-measure)).

Example 39 Type 2 SOF

(Action A) The following can be combined: the building blockdipropylcarbonate [segment=carbonyl [—C(═O)—]; Fg=propoxy (CH₃CH₂CH₂O—);4.38 g, 30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg=hydroxyl (—OH); 3.24 g, 20 mmol] and catalystsodium methoxide (38 mg) and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andheated for 40 min.

Example 40 Type 2 SOF

(Action A) The following can be combined: the building blockdipropylcarbonate [segment=carbonyl [—C(═O)—]; Fg=propoxy (CH₃CH₂CH₂O—);4.38 g, 30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment cyclohexane; Fg=hydroxyl (—OH); 3.24 g, 20 mmol]; phosphoricacid (2 M aq, 100 mg); and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andleft to heat for 40 min.

Example 41 Type 2 SOF

(Action A) The following can be combined: the building block1,1′-carbonyldiimidazole [segment=carbonyl [—C(═O)—]; Fg=imidazole; 4.86g, 30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg=hydroxyl (—OH); 3.24 g, 20 mmol] and catalystsodium methoxide (38 mg) and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andleft to heat for 40 min.

Example 42 Type 2 SOF

(Action A) The following can be combined: the building blockcarbonyldiimidazole [segment=carbonyl [—C(═O)—]; Fg=imidazole; 4.86 g,30 mmol] and the building block 1,3,5-trihydroxycyclohexane[segment=cyclohexane; Fg=hydroxyl (—OH); 3.24 g, 20 mmol]; phosphoricacid (2 M aq, 100 mg); and N-methyl-2-pyrrolidinone (25.5 g). Themixture is mixed on a rolling wave rotator for 10 min and filteredthrough a 1 micron PTFE membrane. (Action B) The reaction mixture isapplied to the reflective side of a metalized (TiZr) MYLAR™ substrateusing a constant velocity draw down coater outfitted with a bird barhaving a 5 mil gap. (Action C) The substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 200° C. andleft to heat for 40 min.

Example 43 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g, 20 mmol] andthe building block 1,6-hexanediol [segment=hexane; Fg=hydroxyl (—OH);3.55 g, 30 mmol]; phosphoric acid (2 M aq, 100 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 44 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g, 20 mmol] andthe building block 1,6-hexanediol [segment=hexane; Fg=hydroxyl (—OH);3.55 g, 30 mmol]; N,N-dimethyl-4-aminopyridine (50 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 45 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g, 20 mmol] andthe building block hexamethylenediamine [segment=hexane; Fg=amine(—NH₂); 3.49 g, 30 mmol]; phosphoric acid (2 M aq, 100 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 46 Type 2 SOF

(Action A) The following can be combined: the building block trimesicacid [segment=1,3,5-benzenetricarboxylate; Fg=H; 4.20 g, 20 mmol] andthe building block hexamethylenediamine [segment=hexane; Fg=hydroxyl(—NH₂); 3.49 g, 30 mmol]; N,N-dimethyl-4-aminopyridine (50 mg); andN-methyl-2-pyrrolidinone (25.5 g). The mixture is mixed on a rollingwave rotator for 10 min and filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture is applied to the reflective side of ametalized (TiZr) MYLAR™ substrate using a constant velocity draw downcoater outfitted with a bird bar having a 5 mil gap. (Action C) Thesubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 200° C. and left to heat for 40 min.

Example 47 Type 2 SOF

(Action A) Preparation of liquid containing reaction mixture. Thefollowing can be combined: the building block 1,4-diisocyanatobenzene[segment=phenyl; Fg=isocyanate (—N═C═O); (0.5 g, 3.1 mmol)] and a secondbuilding block 4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethanol[segment=(4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethyl); (0.69, 2.1mmol)] 10.1 g of dimethylformamide, and 1.0 g of triethylamine. Themixture is stirred until a homogenous solution is obtained. Upon coolingto room temperature, the solution is filtered through a 0.45 micron PTFEmembrane. (Action B) The reaction mixture is to be applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 8 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 120 min.

Example 48 Type 2 SOF

(Action A) Preparation of liquid containing reaction mixture. Thefollowing can be combined: the building block 1,4-diisocyanatohexane[segment=hexyl; Fg=isocyanate (—N═C═O); (0.38 g, 3.6 mmol)] and a secondbuilding block triethanolamine [segment=triethylamine; (0.81, 5.6 mmol)]10.1 g of dimethylformamide, and 1.0 g of triethylamine. The mixture isstirred until a homogenous solution is obtained. Upon cooling to roomtemperature, the solution is filtered through a 0.45 micron PTFEmembrane. (Action B) The reaction mixture is to be applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 8 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer israpidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 120 min.

Example 49 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 4.24 g] and the building blockN,N′-diphenyl-N,N′-bis-(3-hydroxyphenyl)-terphenyl-4,4′-diamine[segment=N,N,N′,N′-tetraphenyl-terphenyl-4,4′-diamine; Fg=hydroxyl(—OH); 5.62 g]; the additives Cymel303 (530 mg) and Silclean 3700 (420mg), and the catalyst Nacure XP-357 (530 mg) and 1-methoxy-2-propanol(41.62 g). The mixture was mixed on a rolling wave rotator for 10 minand then heated at 55° C. for 65 min until a homogenous solutionresulted. The mixture was placed on the rotator and cooled to roomtemperature. The solution was filtered through a 1 micron PTFE membrane.(Action B) The reaction mixture was applied to a commercially available,30 mm drum photoreceptor using a cup coater (Tsukiage coating) at apull-rate of 485 mm/min. (Action C) The photoreceptor drum supportingthe wet layer was rapidly transferred to an actively vented ovenpreheated to 140° C. and left to heat for 40 min. These actions provideda SOF having a thickness of 6.2 microns.

Example 49 Type 2 SOF Attempt

(Action A) Attempted preparation of the liquid containing reactionmixture. The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 5.12 g]; the additives Cymel303 (55 mg), Silclean 3700(210 mg), and 1-methoxy-2-propanol (13.27 g). The mixture was heated to55° C. for 65 min in an attempt to fully dissolve the molecular buildingblock. However it did not fully dissolve. A catalyst Nacure XP-357 (267mg) was added and the heterogeneous mixture was further mixed on arolling wave rotator for 10 min. In this Example, the catalyst was addedafter the heating step. The solution was not filtered prior to coatingdue to the amount of undissolved molecular building block. (Action B)Deposition of reaction mixture as a wet film. The reaction mixture wasapplied to a commercially available, 30 mm drum photoreceptor using acup coater (Tsukiage coating) at a pull-rate of 240 mm/min. (Action C)Promotion of the change of the wet film to a dry film. The photoreceptordrum supporting the wet layer was rapidly transferred to an activelyvented oven preheated to 140° C. and left to heat for 40 min. Theseactions did not provide a uniform film. There were some regions where anon-uniform film formed that contained particles and other regions whereno film was formed at all.

Example 50 Type 2 SOF

(Action A) The following were combined: the building blocktris-[(4-hydroxymethyl)-phenyl]-amine [segment=tri-(p-tolyl)-amine;Fg=hydroxy (—OH); 5.12 g]; the additives Cymel303 (55 mg) and Silclean3700 (210 mg), and the catalyst Nacure XP-357 (267 mg) and1-methoxy-2-propanol (13.27 g). The mixture was mixed on a rolling waverotator for 10 min and then heated at 55° C. for 65 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. It was noted that the viscosity of the reaction mixtureincreased after the heating step (although the viscosity of the solutionbefore and after heating was not measured). (Action B) The reactionmixture was applied to a commercially available, 30 mm drumphotoreceptor using a cup coater (Tsukiage coating) at a pull-rate of240 mm/min. (Action C) The photoreceptor drum supporting the wet layerwas rapidly transferred to an actively vented oven preheated to 140° C.and left to heat for 40 min. These actions provided a SOF having athickness of 6.9 microns.

Example 51 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 1.84 g] and the building block3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropan-1-ol[segment 3,3′-(4,4′-(biphenyl-4-ylazanediyl)bis(4,1-phenylene))dipropyl;Fg=hydroxy (—OH); (2.41 g] and a catalyst p-toluenesulphonic acid (10 wt% solution in dowanol, 460 mg) and 1-methoxy-2-propanol (16.9g—containing 50 ppm DC510). The mixture was mixed on a rolling waverotator for 5 min and then heated at 70° C. for 30 min until ahomogenous solution resulted. The mixture was placed on the rotator andcooled to room temperature. The solution was filtered through a 1 micronPTFE membrane. (Action B) The reaction mixture was applied to aproduction-coated web photoreceptor with a Hirano web coater. Syringepump speed: 4.5 mL/min. (Action C) The photoreceptor supporting the wetlayer was fed at a rate of 1.5 m/min into an actively vented ovenpreheated to 130° C. for 2 min These actions provided a SOF overcoatlayer having a thickness of 2.1 microns on a photoreceptor.

Example 52 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 5.0 g] and the building block benzenedimethanol [segment=p-xylyl;Fg=hydroxyl (—OH); 2.32 g] and a catalyst p-toluenesulphonic acid (10 wt% solution in dowanol, 720 mg) and 1-methoxy-2-propanol (22.5g—containing 50 ppm DC510). The mixture was mixed on a rolling waverotator for 5 min and then heated at 40° C. for 5 min until a homogenoussolution resulted. The mixture was placed on the rotator and cooled toroom temperature. The solution was filtered through a 1 micron PTFEmembrane. (Action B) The reaction mixture was applied to aproduction-coated, production web photoreceptor a Hirano web coater.Syringe pump speed: 5 mL/min. (Action C) The photoreceptor supportingthe wet layer was fed at a rate of 1.5 m/min into an actively ventedoven preheated to 130° C. for 2 min. These actions provided a SOFovercoat layer having a thickness of 2.2 microns on a photoreceptor.

Example 53 Type 2 SOF

(Action A) The following were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine[segment=N,N,N′,N′-tetra-(p-tolyl)biphenyl-4,4′-diamine; Fg=hydroxy(—OH); 5.0 g] and the building block benzenedimethanol [segment=p-xylyl;Fg=hydroxyl (—OH); 2.32 g] and a catalyst p-toluenesulphonic acid (10 wt% solution in dowanol, 720 mg) and 1-methoxy-2-propanol (22.5g—containing 50 ppm DC510). The mixture was mixed on a rolling waverotator for 5 min and then heated at 40° C. for 5 min until a homogenoussolution resulted. The mixture was placed on the rotator and cooled toroom temperature. The solution was filtered through a 1 micron PTFEmembrane. (Action B) The reaction mixture was applied to aproduction-coated, production web photoreceptor with a Hirano webcoater. Syringe pump speed: 10 mL/min. (Action C) The photoreceptorsupporting the wet layer was fed at a rate of 1.5 m/min into an activelyvented oven preheated to 130° C. for 2 min. These actions provided a SOFovercoat layer having a thickness of 4.3 microns on a photoreceptor.

Example 54

(Action A) The following were combined: the building4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethanol[segment=(4,4′,4″-nitrilotris(benzene-4,1-diyl)trimethyl); Fg=alcohol(—OH); (1.48 g, 4.4 mmol)], 0.5 g water and 7.8 g of 1,4-dioxane. Themixture was shaken and heated to 60° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.15 g of a 10 wt % solution ofp-toluenesulfonic acid in 1,4-dioxane to yield the liquid containingreaction mixture. (Action B) The reaction mixture was applied to thereflective side of a metalized (TiZr) MYLAR™ substrate using a constantvelocity draw down coater outfitted with a bird bar having a 15 mil gap.(Action C) The metalized MYLAR™ substrate supporting the wet layer wasrapidly transferred to an actively vented oven preheated to 130° C. andleft to heat for 40 min. These actions provided SOF having a thicknessranging from about 4-10 microns that could be delaminated from substrateas a single free-standing film. The color of the SOF was green.Two-dimensional X-ray scattering data is provided in FIG. 15. As seen inFIG. 15, 2θ is about 17.8 and d is about 4.97 angstroms, indicating thatthe SOF possesses molecular order having a periodicity of about 0.5 nm.

Example 55 Type 2 SOF

(Action A) The following can be combined: the building block4-hydroxybenzyl alcohol [segment=toluene; Fg=hydroxyl (—OH); (0.0272 g,0.22 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH3); (0.0728 g, 0.11 mmol)], and 0.88 g of1-methoxy-2-propanol and 0.01 g of a 10 wt % solution of silclean in1-methoxy-2-propanol. The mixture is shaken and heated to 55° C. until ahomogenous solution is obtained. Upon cooling to rt, the solution isfiltered through a 0.45 micron PTFE membrane. To the filtered solutionis added an acid catalyst delivered as 0.01 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the aluminum substrate using a constant velocity draw down coateroutfitted with a bird bar having a 5 mil gap. (Action C) The aluminumsubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 140° C. and left to heat for 40 min.

Example 56 Type 2 SOF

(Action A) The following can be combined: the building block4-(hydroxymethyl)benzoic acid [segment=4-methylbenzaldehyde; Fg=hydroxyl(—OH); (0.0314 g, 0.206 mmol)] and a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH3); (0.0686 g, 0.103 mmol)], and 0.88 g of1-methoxy-2-propanol and 0.01 g of a 10 wt % solution of silclean in1-methoxy-2-propanol. The mixture is shaken and heated to 55° C. until ahomogenous solution is obtained. Upon cooling to rt, the solution isfiltered through a 0.45 micron PTFE membrane. To the filtered solutionis added an acid catalyst delivered as 0.01 g of a 10 wt % solution ofp-toluenesulfonic acid in 1-methoxy-2-propanol to yield the liquidcontaining reaction mixture. (Action B) The reaction mixture was appliedto the aluminum substrate using a constant velocity draw down coateroutfitted with a bird bar having a 5 mil gap. (Action C) The aluminumsubstrate supporting the wet layer is rapidly transferred to an activelyvented oven preheated to 140° C. and left to heat for 40 min.

Example 57 Type 2 SOF

(Action A) The following were combined: the building block 1,4diaminobenzene [segment=benzene; Fg=amine (—NH₂); (0.14 g, 1.3 mmol)]and a second building block 1,3,5-triformylbenzene [segment=benzene;Fg=aldehyde (—CHO); (0.144 g, 0.89 mmol)], and 2.8 g of NMP. The mixturewas shaken until a homogenous solution resulted. Upon cooling to roomtemperature, the solution was filtered through a 0.45 micron PTFEmembrane. To the filtered solution was added an acid catalyst deliveredas 0.02 g of a 2.5 wt % solution of p-toluenesulfonic acid in NMP toyield the liquid containing reaction mixture. (Action B) The reactionmixture was applied quartz plate affixed to the rotating unit of avariable velocity spin coater rotating at 1000 RPM for 30 seconds.(Action C) The quartz plate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 180° C. and left toheat for 120 min. These actions provide a yellow film having a thicknessof 400 nm that can be delaminated from substrate upon immersion inwater.

It will be appreciated that several of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Variouspresently unforeseen or unanticipated alternatives, modifications,variations or improvements therein may be subsequently made by thoseskilled in the art which are also intended to be encompassed by thefollowing claims. Unless specifically recited in a claim, steps orcomponents of claims should not be implied or imported from thespecification or any other claims as to any particular order, number,position, size, shape, angle, color, or material.

1. A structured organic film (SOF) comprising a plurality of segmentsincluding at least a first segment type and a plurality of linkersincluding at least a first linker type arranged as a covalent organicframework (COF), wherein the SOF is a substantially defect-free film,and the first segment type and/or the first linker type comprises atleast one atom that is not carbon.
 2. The SOF of claim 1, wherein theplurality of segments consists of segments having the first segment typecomprising at least one atom that is not carbon, and the plurality oflinkers consists of linkers of the first linker type.
 3. The SOF ofclaim 1, wherein the plurality of segments comprises at least the firstsegment type comprising at least one atom that is not carbon and asecond segment type that is structurally different from the firstsegment type.
 4. The SOF of claim 1, wherein the plurality of linkerscomprises at least the first linker type comprising at least one atomthat is not carbon and a second linker type that is structurallydifferent from the first linker type.
 5. The SOF of claim 1, wherein theplurality of segments have a core selected from the group consisting ofcarbon, nitrogen, silicon, or phosphorous atomic cores, alkoxy cores;aryl cores; carbonate cores; carbocyclic cores; carbobicyclic cores;carbotricyclic cores; and oligothiophene cores.
 6. The SOF of claim 1,wherein the plurality of linkers are selected from the group consistingof single atom linkers, single covalent bond linkers, double covalentbond linkers, ester linkers, ketone linkers, amide linkers, aminelinkers, imine linkers, ether linkers, urethane linkers, and carbonateslinkers.
 7. The SOF of claim 1, wherein the at least one atom of anelement that is not carbon is selected from the group consisting ofhydrogen, oxygen, nitrogen, silicon, phosphorous, selenium, fluorine,boron, and sulfur.
 8. The SOF of claim 1, wherein the SOF has less than10 pinholes, pores or gaps greater than about 250 nanometers in diameterper cm².
 9. The SOF of claim 1, wherein the SOF is a defect-free SOF.10. The SOF of claim 1, wherein the SOF is periodic.
 11. A process forpreparing a structured organic film (SOF) comprising: (a) preparing aliquid-containing reaction mixture comprising a plurality of molecularbuilding blocks each comprising a segment and a number of functionalgroups; (b) depositing the reaction mixture as a wet film; and (c)promoting change of the wet film to form a dry SOF.
 12. The process ofclaim 11, further comprising promoting a reaction of the functionalgroups, wherein no byproduct is formed as a result of the reaction ofthe functional groups.
 13. The process of claim 11, wherein the SOF isformed after the wet film is exposed to oven drying or infraredradiation (IR) or oven drying and IR drying.
 14. The process of claim11, wherein the reaction mixture is deposited as a wet film on asubstrate.
 15. The process of claim 14, further comprising removing thedry SOF from the substrate to obtain a free-standing SOF.
 16. Theprocess of claim 14, wherein the substrate is a SOF substrate.
 17. Theprocess of claim 16, further comprising chemically attaching the dry SOFto the SOF substrate by either covalent or ionic bonds.
 18. The processof claim 11, further comprising promoting a reaction of the functionalgroups, wherein a volatile byproduct is formed as a result of thereaction of the functional groups.
 19. A process for preparing astructured organic film (SOF) comprising: (a) preparing aliquid-containing reaction mixture comprising a plurality of molecularbuilding blocks each comprising a segment and a number of functionalgroups; (b) depositing the reaction mixture as a wet film on asubstrate; (c) promoting change of the wet film to form a dry SOF; and(d) removing the dry SOF from the substrate to obtain a singlefree-standing SOF.
 20. The SOF of claim 1, wherein the SOF is amono-segment thick layer with a thickness of from about 10 Angstroms toabout 250 Angstroms; or the SOF is a multi-segment thick layer with athickness of from about 20 nm to about 5 mm.
 21. A structured organicfilm (SOF) comprising a plurality of segments including at least a firstsegment type and a plurality of linkers including at least a firstlinker type arranged as a covalent organic framework (COF), wherein theSOF is a substantially defect-free film, and the first segment typeand/or the first linker type comprises a hydrogen.
 22. The SOF of claim21, wherein the plurality of segments consists of segments having thefirst segment type comprising a hydrogen atom, and the plurality oflinkers consists of linkers of the first linker type.
 23. The SOF ofclaim 21, wherein the plurality of segments comprises at least the firstsegment type comprising a hydrogen atom and a second segment type thatis structurally different from the first segment type.
 24. The SOF ofclaim 21, wherein the plurality of linkers comprises at least the firstlinker type comprising a hydrogen and a second linker type that isstructurally different from the first linker type.
 25. The SOF of claim21, wherein the plurality of segments have a core selected from thegroup consisting of carbon, nitrogen, silicon, or phosphorous atomiccores, alkoxy cores, aryl cores, carbonate cores, carbocyclic cores,carbobicyclic cores, carbotricyclic cores, and oligothiophene cores; orthe plurality of linkers are selected from the group consisting ofsingle atom linkers, single covalent bond linkers, double covalent bondlinkers, ester linkers, ketone linkers, amide linkers, amine linkers,imine linkers, ether linkers, urethane linkers, and carbonates linkers.26. The SOF of claim 21, wherein the plurality of segments and/or theplurality of linkers comprises at least one atom selected from the groupconsisting of oxygen, nitrogen, silicon, phosphorous, selenium,fluorine, boron, and sulfur.
 27. The SOF of claim 21, wherein the SOFhas less than 10 pinholes, pores or gaps greater than about 250nanometers in diameter per cm².
 28. The SOF of claim 21, wherein the SOFis a defect-free SOF.
 29. The SOF of claim 21, wherein the SOF isperiodic.
 30. The SOF of claim 21, wherein the SOF is a mono-segmentthick layer with a thickness of from about 10 Angstroms to about 250Angstroms; or the SOF is a multi-segment thick layer with a thickness offrom about 20 nm to about 5 mm.